CN1261608A - 制备聚酯树脂的方法 - Google Patents

制备聚酯树脂的方法 Download PDF

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CN1261608A
CN1261608A CN99122966A CN99122966A CN1261608A CN 1261608 A CN1261608 A CN 1261608A CN 99122966 A CN99122966 A CN 99122966A CN 99122966 A CN99122966 A CN 99122966A CN 1261608 A CN1261608 A CN 1261608A
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titanium
polycondensation
acid
vibrin
dianhydride
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H·阿尔加塔
E·巴利科
A·吉奥范尼尼
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Sinco Ricerche SpA
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/80—Solid-state polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Materials For Medical Uses (AREA)

Abstract

制备芳族聚酯树脂的方法,其中从利用钛化合物作为催化剂所进行的在熔化态下的缩聚阶段中获得的树脂在四羧酸的二酐存在下进行固体缩聚反应。

Description

制备聚酯树脂的方法
本发明涉及生产具有高特性粘度的聚酯树脂的改进方法。
一般用于芳族聚酯树脂在熔化态下的缩聚反应中的催化剂常常是锑的化合物(主要以氧化锑和三乙酸锑形式使用)。基于氧化锗的催化剂也可以使用，但仅仅在某些情况下得到高成本的催化剂。
钛化合物(尤其烷氧基钛)也被建议作为催化剂。这些催化剂具有高活性但导致形成泛黄的聚合物而且由于在从对苯二甲酸合成PET的过程中的水解作用而具有不稳定性。树脂的固态缩聚的动力学因钛化合物的存在而更受到不利影响。由于这些缺点，钛催化剂实际上并没有多大用处。
当前市场的趋势和保护环境的权威部门更坚定地要求PET具有低的残余金属催化剂含量。然而，实际上不可能减少锑催化剂的量，因为它们的活性不是非常的高。
钛催化剂的使用不令人满意，因为它们在固体缩聚反应中的活性低。
所以仍然需要比锑的催化剂更便宜的催化剂，它对健康无害且得到良好的催化剂活性但没有使聚合物着色的诸多可能存在的问题。
最近，按Ti/Si比例9∶1的二氧化钛和硅石，和四异丙基(二辛基)钛酸酯亚磷酸酯(tetraisopropyl(dioctyl)titanate phosphite)被建议作为与烷氧基钛相比很少有泛黄问题的耐水解性催化剂。这些催化剂的活性(以重量ppm的Ti/kg的聚合物表达)远高于锑氧化物或三乙酸盐所获得的活性。
这些催化剂也具有严重的缺点：它们的实际应用被排除了，因为当用于树脂的固体缩聚反应中时它们具有低的动力学。
对于PET的情况，就锑催化剂而言，固体缩聚的动力学是降低了大约50％(同样的条件)。
现在出乎意料地发现，如果固体缩聚是在四羧酸酐(优选芳族)存在下进行，有可能在聚酯树脂的熔化态缩聚反应中使用钛催化剂并获得与使用锑催化剂制得的聚合物的聚合动力学相当或甚至更好的固态缩聚的动力学。
均苯四酸二酐是优选的。二酸酐以约0.05-2wt％的量加入到聚酯树脂中。
固态缩聚反应能够根据已知方法通过在160-230℃之间的温度下操作足以使起始树脂的特性粘度提高至少0.1dl/g的时间来进行。起始树脂的特性粘度一般是0.4-0.7dl/g。然而，有可能从粘度低于0.4dl/g，例如0.2-0.3dl/g的树脂开始。
二酸酐与熔化态的树脂的混合操作例如在挤出机中以较短的停留时间(几十秒)进行。
聚酯树脂的熔化态缩聚反应是根据常规方法通过使用一定用量的钛催化剂实现的，该用量等于相对于聚合物的20-200ppm(wt)钛。
由于钛的催化活性大大高于锑催化剂所达到的活性(更少ppm的金属/每kg聚合物)，对于使用同样ppm的金属有可能减少熔化态下的缩聚时间，因此提高了装置的生产率。
可用作催化剂的钛化合物一般包括烷氧基钛，尤其四乙氧基钛，四丙氧基钛和四丁氧基钛，和四异丙基(二辛基)钛酸酯亚磷酸酯和钛的乙酰基丙酮酸盐，如乙酰基丙酮基钛和二乙酰基乙酰氧基钛和二氧化钛-硅石混合物。
聚酯树脂(在它的合成中可使用钛催化剂)是根据已知方法从具有2-12个碳原子的二醇与芳族二羧酸(优选对苯二甲酸)通过缩聚获得或通过低级脂族二酯(优选对苯二甲酸二甲酯)的酯基转移和随后的缩聚反应获得。可以使用的二醇是乙二醇，丙二醇，丁二醇和1，4-环己烷二甲醇。
优选的树脂是聚对苯二甲酸乙二醇酯和对苯二甲酸乙二醇酯共聚物，其中至多20wt％的从对苯二甲酸形成的单元被间苯二甲酸和/或萘二羧酸的单元取代。
根据本发明方法获得的聚酯树脂在常用聚酯树脂的所有领域中能够找到用途。它们特别可由注射吹塑或挤出吹塑方法制备容器和用于发泡材料的制备中。
在表1中记录了对苯二甲酸双羟乙基酯(BHET)的缩聚条件和通过使用钛催化剂(二氧化钛和硅石的混合物；Ti/Si比9∶1；C-94，购自Akzo Nobel)和锑催化剂(购自Atochem的三乙酸锑)获得的结果。表1
                 用锑试验       用钛试验缩聚温度(℃)            267            267(起始值)真空(毫巴)              1-5            1.0缩聚时间           4小时30分钟     4小时30分钟最终缩聚温度(℃)        269            270催化剂的量              240            60(ppm金属)特性粘度(dl/g)          0.653          0.673活性IVf/hr*ppm Me)    0.002481       0.000602活性Ti/活性Sb           4.123077        -端酸基Eq/T              13             13.8彩色指数L*             71             76
    a*            -2.86          -2.48
    b*            -1.27           4.73
从表中数据可以看出，钛催化剂的活性比锑催化剂的活性高4倍(活性以特性粘度增量/每ppm金属/每小时反应表达)。
用钛催化剂获得的聚合物的彩色指数b*大大高于含锑催化剂的聚合物中的彩色指数(然而该缺点可通过向催化剂中添加较小百分数的钴化合物或其它有机色料而容易地克服)。
在表2中记录了与用锑催化剂获得的聚合物和用钛催化剂获得的聚合物的固体缩聚(在氮气流中195℃)有关的I.V.数据。
表2
        用锑试验    用钛试验时间        没有    有0.4wt％   没有    有0.4wt％(小时)      PMDA    PMDA        PMDA     PMDA0          0.653   0.653       0.673    0.6732          0.717   0.804       0.695    0.8454          0.754   1.020       0.732    0.9826          0.813   1.328       0.755    1.350
表3
                  用锑试验    用钛试验缩聚温度(℃)           267           267真空(毫巴)             1-2           1-2缩聚时间            4小时15分钟      5小时最终缩聚温度(℃)       270           270催化剂的量(ppm金属)    219           28特性粘度(dl/g)         0.670         0.655活性(IVf/hr*ppm Me)  0.000737      0.0046429活性Ti/活性Sb          6.2980011端酸基Eq/T             27.20         21.23彩色指数L*            67.74         70.14
    a*           -3.03         -2.92
    b*           -1.52          5.24
分析测量
根据ASTM D4603-86，在25℃下，以0.5g树脂在100ml的由苯酚和四氯乙烷按60/40(wt)比例组成的混合物中的溶液来测量聚酯树脂的特性粘度。

Claims (4)

1、从特性粘度为0.2-0.7dl/g的树脂开始制备特性粘度高于0.7dl/g的聚酯树脂的方法，该起始聚酯是通过具有2-12个碳原子的二醇与芳族二羧酸的缩聚反应或通过二羧酸的低级烷基酯的酯基转移反应和随后的缩聚反应获得，在缩聚阶段中使用包括钛化合物的催化剂，其特征在于从缩聚反应中获得的聚酯树脂与四羧酸的二酐一起被加入并随后进行固态缩聚反应以使特性粘度提高了至少0.1dl/g。
2、根据权利要求1的方法，其中钛化合物选自烷氧基钛，钛的乙酰基丙酮酸盐，钛的二氧化物和钛酸酯亚磷酸酯。
3、根据权利要求1或2的方法，其中二酐是均苯四酸二酐。
4、根据权利要求1-3中任何一项的方法，其中聚酯树脂是聚对苯二甲酸乙二醇酯和对苯二甲酸乙二醇酯共聚物，其中至多20wt％的从对苯二甲酸形成的单元被从间苯二甲酸和/或萘二羧酸形成的单元取代。
CN99122966A 1998-12-23 1999-12-22 制备聚酯树脂的方法 Pending CN1261608A (zh)

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