CN1317030A - 高粘度聚酯的制备方法 - Google Patents
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Abstract
本发明涉及制备酸端基含量较低的高粘度聚酯的方法。先生产由低粘度聚酯与噁唑啉类组成的母料，然后将其与高粘度聚酯混合。该混合物(干掺合物)随后进行进一步加工。
Description
本发明涉及一种制备酸端基含量减少的高粘度聚酯的方法，按此法，由低粘度聚酯与噁唑啉类制备母料(masterbatch)，然后该母料与高粘度聚酯混合，该混合物(干掺合物)再接受进一步加工。
羧端基被掩蔽的聚酯是已知的。为此，可采用各种各样能与羧基基团起反应的化合物来掩蔽羧端基。
譬如已知，带游离羧端基的聚酯可与噁唑啉类起反应，其间噁唑啉环被打开(US-A 4 351 936、DE-A 42 25 627)。例如，2-位上取代的Δ2-噁唑啉类可与羧基基团起反应生成氨基乙醇的酯-酰胺(《化学评论》71,483～505,1971以及《应用化学(德)》78,913-927,1966)。
另一种掩蔽羧基基团的方法包括：带游离羧端基的聚酯与环氧化物起反应，由该羧基基团生成酯基团(BP 1 139 379)。又已知一种通过与碳化二亚胺类起反应来掩蔽羧基基团的方法(US-A 3 193 522、US-A 3 193 523、US-A 38 35 098)。按此法，首先由羧基基团生成单酰化脲，该酰化脲再通过进一步重排达到稳定化。最后提到的2种方法的严重缺陷是，掩蔽试剂以及所生成的重排和裂解产物有较高毒性，因此实施掩蔽反应时必须遵守特殊安全防范规定。
还知道利用与聚碳酸酯的反应掩蔽聚酯羧端基的方法(US-A 3563 847、EP 0 486 916 B1)。在这种情况下，聚碳酸酯单元通过酯基团键合到聚酯分子上。
掩蔽反应的目的是减少聚酯的游离羧基基团数目。羧端基数目减少的聚酯显示出对水解稳定性的显著改善。酸端基含量减少的聚酯还表现出在机械应力下较好的热稳定性和耐化学侵蚀。采用多官能掩蔽试剂可提高聚酯的分子量。
例如，已知可按下列方法用噁唑啉类掩蔽羧端基：
1．在聚酯树脂的制备中，熔融缩聚反应结束并已达到要求分子量以后，加入掩蔽试剂。
2．掩蔽试剂与聚酯粒料进行混合，然后通过混炼步骤结合到聚酯中去。
上述方法的缺点是，它们仅适合稳定低缩合度的低粘度聚酯。鉴于技术和动力学的原因，高聚合度(高分子量)的高粘度聚酯通常采用由低粘度聚酯为基础的树脂出发的“固相后缩合”来制备。伴随聚酯熔融过程的进一步加工步骤，往往会导致后缩合所获聚酯分子量的降解，因而导致机械及物理性能的恶化。
上面所描述的通过混炼将噁唑啉掩蔽试剂结合到聚酯中去的方法存在另一个缺点，这就是，为在混炼步骤的典型时间内达到酸端基含量足够程度的降低，噁唑啉类，这里尤其指苯基取代的噁唑啉类，在反应性上不令人满意。
现已发现一种制备羧端基含量减少、(耐)水解稳定性改善，因此不发生分子量降解的高粘度聚酯树脂的方法。本发明聚酯另外还具有在机械应力下较好的热稳定性和耐化学侵蚀。
本发明方法的一个优点在于，为将噁唑啉结合到高粘度聚酯中去不需要对高粘度聚酯实施会造成聚酯损伤的额外熔融步骤。与此同时，依靠2个熔融态加工步骤便为掩蔽试剂(噁唑啉)掩蔽羧端基提供足够长的反应时间。本发明方法的另一个优点在于，当采用多官能噁唑啉类时，观察到高粘度聚酯分子量的增加。
因此，本发明提供一种制备高粘度聚酯的方法，其特征在于，低粘度聚酯与噁唑啉化合物(构成)的母料与高粘度聚酯进行混合形成一种干掺合物，然后干掺合物再进一步加工。干掺合物在这里是指一种固态热塑性塑料(粒料或粉末)的物理混合物。
低粘度聚酯与噁唑啉化合物的母料是通过各个组分的混合，然后对混合物进行混炼制成的。各个组分的混合是按传统方法在介于0～50℃(优选室温)的温度进行的。混炼操作通常在170～380℃，优选200～220℃的温度进行。
高粘度聚酯与由低粘度聚酯和噁唑啉构成的母料彼此混合形成干掺合物的过程，可在低于和高于室温的温度进行。该温度可介于0～50℃。混合优选在室温进行。该混合物(干掺合物)的一个优点在于，它具有防止组分分层(demixing)的稳定性。
高粘度聚酯与母料的混合物(干掺合物)的进一步加工按传统方法实施，例如可通过混炼、挤塑、吹塑、挤出吹塑、注塑、捏合或压延来实施，其间温度一般介于200～300℃，所选择的温度范围应与具体加工技术相适应。
混合物(干掺合物)经过进一步加工可制成各种类型粒料、半制品(例如，薄膜、电缆外套、片材、型材、管材)或者模塑件。
高-与低粘度聚酯的“溶液相对粘度”应选择为，使得高-与低粘度聚酯在溶液相对粘度上相差至少0.05，优选至少0.1，尤其优选至少0.15。
本发明的效果在粘度差比这大的多的情况下也能表现出来。可以仅作为例子提及相对粘度差值ηrel可达0.7。
低粘度聚酯的溶液相对粘度(ηrel)一般低于1.90，优选低于1.75。
高粘度聚酯的溶液相对粘度一般大于1.50，优选大于1.75。
溶液相对粘度(ηrel)的测定是采用5g聚合物/L苯酚/邻二氯苯(1∶1重量份)的溶液在25℃的温度进行的。
噁唑啉化合物在母料中的含量一般介于5～60 wt％，优选10～40 wt％(以母料为基准)。
噁唑啉化合物在加工成干掺合物以后的高粘度聚酯中的含量，以聚酯加母料为基准，一般介于0.02～10，优选0.05～5，尤其是0.1～2 wt％。
可加入1种噁唑啉化合物或其多种的混合物。
可采用的噁唑啉化合物例如是在DE-A4 129 980、DE-A 42 25 627和WO 96/11 978中提到的那些。因此，这些专利申请中有关这方面的公开内容并入本发明公开内容。
WO 96/11 978，第14页，最后一段到第17页末尾，以及DE-A 4129 980，第5页，第20行到66行所描述的噁唑啉类是优选使用的。
尤其优选的噁唑啉类是下列通式的单噁唑啉类的各种互变异构形式：
2-噁唑啉类 3-噁唑啉类 4-噁唑啉类以及通式(Ⅳ)的双噁唑啉类其中取代基R2～R6可彼此独立地具有下列含义：
氢原子、烷基、链烯基、芳基、羟烷基、羟芳基、烷氧烷基、烷氧芳基、烷基酯、芳基酯、酰氧基烷基、酰氧基芳基、卤代烷基、卤代芳基、硝基烷基、硝基芳基、苯甲酰氨基烷基、苯甲酰氨基芳基、羟基氨基羰基、全卤代烷基、全卤代芳基、卤素、氨基、乙烯基或巯基基团，其中每种情况的烷基基团具有1～22个碳原子；链烯基基团具有2～22个碳原子；芳基基团具有6～14个碳原子。
不同噁唑啉类的混合物也可使用。在单噁唑啉类当中，优选2-噁唑啉类，尤其是这样的，其中
R2代表烷基、链烯基或羟烷基，
R3、R4代表烷基、羟烷基或烷氧基烷基，以及
R5、R6代表氢原子或烷基或羟烷基等基团，
其中烷基基团优选具有1～18个碳原子；亚烷基基团，2～18个碳原子。
在通式(Ⅳ)的双噁唑啉类当中，特别要提到的的是对称构造的(即，R7=R11,R8=R12,R9=R13以及R10=R14)并且处于芳环的间或对位的那些。特别值得一提的是2,2’-对亚苯基-双(4,4’-二甲基-2-噁唑啉)、2,2’-对亚苯基-双(4-苯基-2-噁唑啉)、2,2’-间-亚苯基-双(2-噁唑啉)、2,2’-间-亚苯基-双(4-甲基-2-噁唑啉)、2,2’-间-亚苯基-双(4,4’-二甲基-2-噁唑啉)以及2,2’-间-亚苯基-双(4-苯基-2-噁唑啉)，乃至2,2’-间-亚苯基-双(4-苯基-2-噁唑啉)，尤其优选2,2’-对亚苯基-双(2-噁唑啉)以及2,2’-间亚苯基-双(2-噁唑啉)。
优选用聚对苯二酸链烷二醇酯作为聚酯。
就本发明内容而言，聚对苯二酸链烷二醇酯是芳族二羧酸或其活性衍生物(例如，二甲酯或酸酐)与脂族、环脂族或芳脂族二醇的反应产物，以及这些反应产物的混合物。
优选的聚对苯二酸链烷二醇酯可由对苯二酸(或其活性衍生物)与2～10个碳原子的脂族或环脂族二醇按已知方法制备(《塑料手册》，卷Ⅷ,p.695起，Carl-Hanser出版社，慕尼黑1973)。
优选的聚对苯二酸链烷二醇酯包含至少80，优选90 mol％，以二羧酸为基准，对苯二酸基团，以及至少80，优选至少90 mol％，以二醇组分为基准，乙二醇、丙-1,3-二醇和/或丁-1,4-二醇基团。
优选的聚对苯二酸链烷二醇酯除了包含对苯二酸基团之外还可包含最高20 mol％具有8～14个碳原子的其他芳族二羧酸的或具有4～12个碳原子的脂族二羧酸的基团，例如下列的基团：邻苯二酸、间苯二酸、萘-2,6-二羧酸、4,4’-二苯基二羧酸、琥珀酸、己二酸或癸二酸、壬二酸或环已烷二乙酸。
优选的聚对苯二酸链烷二醇酯除了包含乙二醇基团和丁-1,4-二醇基团之外，还可包含最高20 mol％3～12个碳原子的其他脂族二醇或6～21个碳原子的环脂族二醇，例如下列的基团：丙-1,3-二醇、2-乙基丙-1,3-二醇、新戊二醇、戊-1,5-二醇、己-1,6-二醇、环己烷-1,4-二甲醇、3-甲基戊-2,4-二醇、2-甲基戊-2,4-二醇、2,2,4-三甲基戊-1,3-二醇以及-1,6-二醇、2-乙基己-1,3-二醇、2,2-二乙基丙-1,3-二醇、己-2,5-二醇、1,4-二(β-羟乙氧基)-苯、2,2-双(4-羟基环己基)-丙烷、2,4-二羟基-1,1,3,3-四甲基-环丁烷、2,2-双(3-β-羟基乙氧基苯基)-丙烷以及2,2-双(4-羟基丙氧基苯基)-丙烷(DE-OS 24 07 674、24 07 776、27 15 932)。
聚对苯二酸链烷二醇酯可通过结合进较少量三-或四-羟基醇或三-或四-元羧酸而实现支化，例如描述在DE-OS 19 00 270和US-A 3692 744中。优选的支化剂的例子是1,3,5-苯三酸、偏苯三酸、三羟甲基乙烷和-丙烷，以及季戊四醇。
建议使用，以酸组分为基准不超过1 mol％的支化剂。
尤其优选的聚对苯二酸链烷二醇酯是唯一地使用对苯二酸及其活性衍生物(例如，其二烷基酯)与乙二醇、丙-1,3-二醇和/或丁-1,4-二醇(聚对苯二酸乙二醇酯和聚对苯二酸丁二醇酯)所制备的那些，以及这些聚对苯二酸链烷二醇酯的混合物。
优选的聚对苯二酸链烷二醇酯也可以是由至少2种上述酸组分和/或至少2种上述醇组分制备的共聚聚酯，尤其优选的共聚聚酯是聚对苯二酸(乙二醇/丁-1,4-二醇)酯。
高-与低粘度聚酯的混合物也可使用。
传统添加剂，例如润滑剂和脱模剂、成核剂、抗静电剂、颜料、稳定剂以及耐焰添加剂，可在进一步加工期间加入。
根据其综合性能类别之不同，以低酸端基含量的高粘度聚酯为基础的热塑性模塑组合物可用于各种不同领域，例如作为光波导体的外鞘、电缆外鞘，用于汽车行业、电气工程以及休闲和运动业。
实施例
母料的制备
20 wt％1,3-PBO与80 wt％溶液相对粘度ηrel等于1.66的低粘度聚对苯二甲酸丁二醇酯(PBT)在室温下进行混合，然后混合物在ZSK 31/1型挤塑机中、物料温度为约180～220℃的条件下进行混炼。
干掺合物的制备
特定数量上述母料在室温下与相应数量溶液相对粘度ηrel等于1.85的高粘度PBT进行混合。有关用量的数据载于表1中。
干掺合物的最终加工
在本例中，干掺合物通过在Arburg 320-210-500型注塑机上在物料温度等于240～280℃、模具温度等于80℃条件下的注塑加工而制成哑铃形试样条(3 mm厚，按ISO 527规定)。试验结果载于表1中。该表中所载全部试验都是对上述哑铃形试样条实施的。
1,3-PBO是2,2’-间亚苯基-双(2-噁唑啉)[IUPAC(国际纯粹与应用化学联合会命名法)：2,2’-(1,3-亚苯基)双(4,5-二氢噁唑)]，由Palmarole公司(Basle，瑞士)提供。
采用5g聚合物溶于1 L苯酚/二氯苯(50 wt％/50 wt％)中的溶液，在25℃测定溶液相对粘度ηrel。羧端基(含量)是通过将样品材料溶解在甲酚/氯仿中然后进行光度滴定而确定的。断裂伸长是在按照DIN 53455的拉伸试验中对上述哑铃形试样条测定的。水解试验的实施过程为：将上述试样放在Varioklav蒸汽消毒罐(型号300/400/500EP-Z)中，在100℃和饱和水蒸气气氛中进行贮存。
从表1中可以看出，本发明方法在经过最终加工步骤之后生产出的材料(A～F)，与标准PBT(对比例1)相比，具有较低酸端基含量、略微增加的粘度以及改善的耐水解稳定性(从高断裂伸长值看出)，同时维持了其他性能。表1中的对比例2显示，本发明方法所达到的优点无法通过在最终加工步骤之前混入纯1,3-PBO来达到。表1
*所有试验，如同在对比例2和A～E中那样，都是对用注塑制备的哑铃形试样条进行的**哑铃形试样条是通过对0.8％纯1,3-PBO(而不是母料)与98.2％PBT的混合物进行注塑制备的n.m.：未测定
| 对比例1* | 对比例2** | A | B | C | D | E | ||
| 高粘度PBT(ηrel=1.85) | [％] | 100 | 98.2 | 99 | 98 | 97 | 96 | 95 |
| 20％1,3-PBO 与 80 wt％低粘度PBT(ηrel=1.66)的母料 | [％] | 0 | - | 1 | 2 | 3 | 4 | 5 |
| 1,3-PBO净含量(计算值) | [％] | 0 | 0.8 | 0.2 | 0.4 | 0.6 | 0.8 | 1.0 |
| ηrel | 1.76 | 1.72 | 1.79 | 1.80 | 1.81 | 1.80 | 1.80 | |
| 羧端基 | [mmol kg-1] | 29 | n.m. | 23 | 18 | 13 | 11 | 8 |
| 水解前断裂伸长 | [％] | 309 | 300 | 308 | 265 | 303 | 311 | 304 |
| 水解(3日)后断裂伸长 | [％] | 100 | 70 | 165 | 232 | 254 | 225 | 180 |
| 水解(7日)后断裂伸长 | [％] | 30 | 20 | 70 | 109 | 92 | 80 | 82 |
| 水解(10日)后断裂伸长 | [％] | 5 | 10 | 23 | 49 | 44 | 49 | 53 |
Claims (15)
1．一种制备高粘度聚酯的方法，其特征在于，低粘度聚酯与噁唑啉化合物构成的母料与固体形式高粘度聚酯进行混合以形成干掺合物，然后干掺合物再进行进一步加工。
2．权利要求1的方法，其特征在于，高-与低粘度聚酯在溶液相对粘度上的差值至少是0.05。
3．权利要求2的方法，其特征在于，该差值至少是0.1。
4．权利要求3的方法，其特征在于，该差值至少是0.15。
5．权利要求1的方法，其特征在于，低粘度聚酯的溶液相对粘度低于1.90；高粘度聚酯的溶液相对粘度大于1.50。
6．权利要求5的方法，其特征在于，低粘度聚酯的溶液相对粘度低于1.75；高粘度聚酯的溶液相对粘度大于1.75。
7．权利要求1的方法，其特征在于，噁唑啉在高粘度聚酯与母料构成的整个混合物中的含量介于0.02～10 wt％。
8．权利要求7的方法，其特征在于，噁唑啉的含量介于0.05～5 wt％。
9．权利要求8的方法，其特征在于，噁唑啉的含量介于0.1～2 wt％。
10．权利要求1的方法，其特征在于，母料是通过低粘度聚酯与噁唑啉进行混合，随后混合物进行混炼而制成的。
11．权利要求1的方法，其特征在于，母料包含5～60 wt％噁唑啉化合物。
12．权利要求1的方法，其中在进一步加工期间加入选自润滑剂和脱模剂、成核剂、抗静电剂、颜料、稳定剂和耐焰剂的添加剂。
13．一种高粘度聚酯，它可采用权利要求1的方法获得。
14．权利要求13的聚酯用于制备各种类型粒料、半制品或模塑件的应用。
15．一种半制品和模塑件，它们可由权利要求13的聚酯获得。
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| DE4225627A1 (de) | 1992-08-03 | 1994-02-10 | Henkel Kgaa | Verfahren zur Modifizierung von Polymeren |
| US5536793A (en) * | 1993-01-29 | 1996-07-16 | Amoco Corporation | Concentrate for use in the melt fabrication of polyester |
| JP3586995B2 (ja) * | 1996-10-08 | 2004-11-10 | 株式会社カネカ | 難燃静電防止性ポリエステル系樹脂組成物 |
-
1998
- 1998-09-15 DE DE19842152A patent/DE19842152A1/de not_active Withdrawn
-
1999
- 1999-09-07 AT AT99944618T patent/ATE240983T1/de not_active IP Right Cessation
- 1999-09-07 AU AU57461/99A patent/AU5746199A/en not_active Abandoned
- 1999-09-07 US US09/786,712 patent/US6515044B1/en not_active Expired - Fee Related
- 1999-09-07 KR KR1020017003266A patent/KR100655839B1/ko not_active IP Right Cessation
- 1999-09-07 EP EP99944618A patent/EP1124884B1/de not_active Expired - Lifetime
- 1999-09-07 CN CN99810827A patent/CN1125110C/zh not_active Expired - Fee Related
- 1999-09-07 ES ES99944618T patent/ES2198955T3/es not_active Expired - Lifetime
- 1999-09-07 DE DE59905680T patent/DE59905680D1/de not_active Expired - Lifetime
- 1999-09-07 JP JP2000570227A patent/JP2002524633A/ja active Pending
- 1999-09-07 WO PCT/EP1999/006575 patent/WO2000015693A1/de active IP Right Grant
-
2002
- 2002-03-22 HK HK02102220.6A patent/HK1040729B/zh not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897158A (zh) * | 2014-04-11 | 2014-07-02 | 扬州金森光电材料有限公司 | Pbt制造工艺 |
| CN103897159A (zh) * | 2014-04-11 | 2014-07-02 | 扬州金森光电材料有限公司 | Pbt生产工艺 |
| CN103897159B (zh) * | 2014-04-11 | 2016-04-20 | 扬州金森光电材料有限公司 | Pbt生产工艺 |
| CN103897158B (zh) * | 2014-04-11 | 2016-04-20 | 扬州金森光电材料有限公司 | Pbt制造工艺 |
| US10301516B2 (en) | 2014-07-22 | 2019-05-28 | Kunshan Tianyang Hot Melt Adhesive Co., Ltd | Method for preparing polyester hot melt adhesive with high viscosity and locally sensitive viscosity-temperature property |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000015693A1 (de) | 2000-03-23 |
| CN1125110C (zh) | 2003-10-22 |
| DE59905680D1 (de) | 2003-06-26 |
| DE19842152A1 (de) | 2000-03-16 |
| HK1040729A1 (en) | 2002-06-21 |
| ES2198955T3 (es) | 2004-02-01 |
| US6515044B1 (en) | 2003-02-04 |
| AU5746199A (en) | 2000-04-03 |
| KR100655839B1 (ko) | 2006-12-12 |
| HK1040729B (zh) | 2004-07-09 |
| KR20010075094A (ko) | 2001-08-09 |
| JP2002524633A (ja) | 2002-08-06 |
| EP1124884B1 (de) | 2003-05-21 |
| EP1124884A1 (de) | 2001-08-22 |
| ATE240983T1 (de) | 2003-06-15 |
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