CN102492128A - Preparation method and use of low-specific-surface-area titanium polyesterification catalyst - Google Patents
Preparation method and use of low-specific-surface-area titanium polyesterification catalyst Download PDFInfo
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- CN102492128A CN102492128A CN2011104142864A CN201110414286A CN102492128A CN 102492128 A CN102492128 A CN 102492128A CN 2011104142864 A CN2011104142864 A CN 2011104142864A CN 201110414286 A CN201110414286 A CN 201110414286A CN 102492128 A CN102492128 A CN 102492128A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010936 titanium Substances 0.000 title claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 92
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 21
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical group COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- -1 silicate ester Chemical class 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域 technical field
本发明涉及的是一种催化剂的制备方法及其应用，特别涉及的是一种利用正硅酸四乙酯和三甲基磷酸酯进行改性的低比表面积钛系聚酯催化剂的制备方法及其应用，属于聚酯催化剂领域。 The present invention relates to a method for preparing a catalyst and its application, in particular to a method for preparing a titanium-based polyester catalyst with a low specific surface area modified by tetraethyl orthosilicate and trimethyl phosphate. The application thereof belongs to the field of polyester catalysts.
背景技术 Background technique
聚酯是一类应用广泛的合成材料，其中聚对苯二甲酸乙二醇酯(PET)由于具有良好的成纤性能，而引人注意。目前，聚酯工业生产中所使用的催化剂主要为锑化合物，如三氧化二锑、醋酸锑、乙二醇锑等。含锑的化合物由于可能会对环境和人体造成危害，而引起人们的广泛关注。目前许多国外PET生产厂商都在致力于开发新型非重金属聚酯催化剂，其中钛系催化剂由于其较高的催化活性而倍受关注。 Polyester is a class of widely used synthetic materials, among which polyethylene terephthalate (PET) has attracted attention due to its good fiber-forming properties. At present, the catalysts used in the industrial production of polyester are mainly antimony compounds, such as antimony trioxide, antimony acetate, and antimony glycol. Compounds containing antimony have attracted widespread attention because they may cause harm to the environment and human body. At present, many foreign PET manufacturers are devoting themselves to the development of new non-heavy metal polyester catalysts, among which titanium-based catalysts have attracted much attention due to their high catalytic activity.
聚酯生产中催化剂至关重要，催化剂的研究一直是聚酯行业的重要课题，国外学者对聚酯生产催化剂及其催化机理曾进行了广泛而深人的研究，发现对缩聚反应有催化作用的化合物种类繁多，几乎涉及了除卤族元素和惰性元素之外的所有主副族元素的化合物。但是目前工业生产应用和研究较多的聚酯催化剂主要是锑系催化剂，其价格适中，价格低廉，因而在聚酯工业中得到了普遍的使用。传统钛系催化剂具有良好的稳定性，具有高活性，但在反应过程中引发的副反应较多，制得的聚酯存在稳定性差和制品泛黄、浑浊的问题，因而一直没有得到大规模使用。 Catalysts are very important in polyester production, and the research on catalysts has always been an important topic in the polyester industry. Foreign scholars have conducted extensive and in-depth research on catalysts for polyester production and their catalytic mechanism, and found that catalysts that can catalyze polycondensation reactions There are many kinds of compounds, involving almost all the compounds of main and subgroup elements except halogen elements and inert elements. However, at present, the polyester catalysts that are widely used in industrial production and research are mainly antimony-based catalysts, which are moderately priced and low in price, so they are widely used in the polyester industry. Traditional titanium-based catalysts have good stability and high activity, but many side reactions are caused during the reaction process, and the polyester produced has problems of poor stability and yellowing and turbidity of the product, so it has not been used on a large scale. .
聚酯的色相L值与聚酯的亮度有关，数值较高为好，一般聚酯的色相L值在60左右；聚酯的色相b值与聚酯反黄有关，数值越低，表明该聚酯越不容易反黄，当色相b值大于3.0，说明生产出来的聚酯越发黄严重，影响聚酯的效果。 The hue L value of polyester is related to the brightness of polyester, and it is better to have a higher value. Generally, the hue L value of polyester is about 60; the hue b value of polyester is related to the anti-yellowness of polyester. The ester is less likely to turn yellow. When the hue b value is greater than 3.0, it means that the produced polyester is more yellow and will affect the effect of polyester.
发明内容 Contents of the invention
由上述内容得知：钛系催化剂催化反应速度过快，导致副反应增多，产生许多副产物，继而聚酯颜色发黄，色相差。 From the above content, it is known that the catalytic reaction speed of the titanium-based catalyst is too fast, which leads to an increase in side reactions and produces many by-products, and then the color of the polyester turns yellow and the hue is poor.
为了解决上述技术中存在一些不足和缺陷，本发明针对上述问题，提供了一种低比表面积钛系聚酯催化剂的制备方法及其应用，具体的是一种通过正硅酸四乙酯和三甲基磷酸酯改性的方法制备该催化剂，使其在催化合成PET聚酯的过程中，通过减小催化剂的比表面积、孔面积和孔体积，继而降低催化剂的催化活性，减少副反应，制得的聚酯产品色相好，同时还能提高钛系催化剂的其他性能。同时不含有毒的锑系化合物，消除了锑系化合物对环境和人体的毒害。由于在微量的水中钛酸异丙酯水解生成白色二氧化钛，水溶性差，不与水发生反应，性质很稳定，故该催化剂具有抗水解性。 In order to solve some deficiencies and defects in the above-mentioned technologies, the present invention aims at the above-mentioned problems, and provides a preparation method and application of a titanium-based polyester catalyst with a low specific surface area. The catalyst is prepared by the method of methyl phosphate modification, so that in the process of catalyzing the synthesis of PET polyester, by reducing the specific surface area, pore area and pore volume of the catalyst, and then reducing the catalytic activity of the catalyst, reducing side reactions, and producing The obtained polyester product has a good hue, and at the same time, other performances of the titanium series catalyst can be improved. At the same time, it does not contain toxic antimony compounds, eliminating the poisonous effects of antimony compounds on the environment and human body. Because isopropyl titanate is hydrolyzed in a small amount of water to produce white titanium dioxide, which has poor water solubility, does not react with water, and has very stable properties, so the catalyst has hydrolysis resistance.
本发明是通过如下技术方案实现的： The present invention is achieved through the following technical solutions:
具体方法如下：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸酯、磷酸酯、硅酸酯和金属化合物溶于有机溶剂中，搅拌，恒温，同时滴加少量的水促进水解，制得的沉淀用丙酮洗涤，除去残留的乙二醇。最后将沉淀在70℃下真空干燥，即得红色粉末催化剂。本发明通过有机改性的方法制备该催化剂，不仅提高了二氧化钛催化剂的催化性能，同时也改善了最终产品的各项性能。 The specific method is as follows: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve titanate, phosphate, silicate and metal compounds in the organic solvent, stir, keep the temperature, and add a small amount of water dropwise to promote hydrolysis , the resulting precipitate was washed with acetone to remove residual ethylene glycol. Finally, the precipitate was vacuum-dried at 70°C to obtain a red powder catalyst. The invention prepares the catalyst through an organic modification method, which not only improves the catalytic performance of the titanium dioxide catalyst, but also improves various properties of the final product.
以下对本发明作出进一步的描述： The present invention is further described below:
1、金属钛酸酯为钛酸异丙酯，是以正丁醇、四氯化钛和氨为原料，在甲苯溶剂中经酯化反应制得的；磷酸酯为三甲基磷酸酯，硅酸酯为正硅酸四乙酯，其它金属化合物为氯化铝； 1. Metal titanate is isopropyl titanate, which is obtained by esterification reaction in toluene solvent with n-butanol, titanium tetrachloride and ammonia as raw materials; phosphoric acid ester is trimethyl phosphate, silicon The acid ester is tetraethyl orthosilicate, and other metal compounds are aluminum chloride;
2、将pH值为8的水慢慢滴加到有机溶剂中，制得红色沉淀，有机溶剂为乙二醇；乙二醇的用量为2500-2600ml/molTi，反应恒定温度为200℃，搅拌的速度为2000-3000r/min；水的用量为250-260ml/molTi，而且水的pH值在8-8.5，滴加的时间在25-30min内； 2. Slowly add water with a pH value of 8 to the organic solvent to obtain a red precipitate. The organic solvent is ethylene glycol; the amount of ethylene glycol is 2500-2600ml/molTi, and the constant reaction temperature is 200°C. Stir The speed is 2000-3000r/min; the amount of water is 250-260ml/molTi, and the pH value of the water is 8-8.5, and the time of dropping is within 25-30min;
3、用丙酮反复洗涤红色沉淀，过滤，最后真空干燥，制得红色粉末催化剂； 3. Wash the red precipitate repeatedly with acetone, filter, and finally vacuum-dry to obtain a red powder catalyst;
4、有机改性剂为三甲基磷酸酯和正硅酸四乙酯，三甲基磷酸酯加入的量与钛酸酯的质量比为9：1，正硅酸四乙酯与钛酸酯的用量摩尔比为1：2，氯化铝与钛酸酯的用量摩尔比为1:10，制备红色沉淀； 4. The organic modifiers are trimethyl phosphate and tetraethyl orthosilicate, the mass ratio of trimethyl phosphate to titanate is 9:1, the ratio of tetraethyl orthosilicate to titanate The molar ratio of the amount used is 1:2, and the molar ratio of the amount of aluminum chloride to titanate is 1:10 to prepare a red precipitate;
5、有机改性剂在制备沉淀过程中加入，更有利于催化剂的改性。 5. The organic modifier is added in the process of preparing the precipitation, which is more conducive to the modification of the catalyst.
该催化剂的活性是原有锑系催化剂的20倍以上，在聚酯合成过程中，其用量为20-30μg/g，催化剂的用量以对苯二甲酸的用量为参考。 The activity of the catalyst is more than 20 times that of the original antimony-based catalyst. In the polyester synthesis process, the dosage is 20-30 μg/g, and the dosage of the catalyst is based on the dosage of terephthalic acid.
催化剂的加入形式并不影响催化剂的活性，因为催化剂的活性是由Ti的含量决定的，催化剂以粉末的形式加入到反应体系。 The addition form of the catalyst does not affect the activity of the catalyst, because the activity of the catalyst is determined by the content of Ti, and the catalyst is added to the reaction system in the form of powder.
本发明通过引入有机改性剂正硅酸四乙酯和三甲基磷酸酯，对催化剂进行改性和设计，减小催化剂的比表面积、孔面积和孔体积，继而降低催化剂的催化活性，减少副反应。该催化剂经试验验证，确实具有实质性的特点和进步，能有效地克服聚酯发黄的问题。 The present invention modifies and designs the catalyst by introducing organic modifiers tetraethyl orthosilicate and trimethyl phosphate, reduces the specific surface area, pore area and pore volume of the catalyst, and then reduces the catalytic activity of the catalyst, reducing side effects. The catalyst has been verified by experiments and indeed has substantial characteristics and progress, and can effectively overcome the problem of polyester yellowing.
下面结合具体的实施例进一步验证本发明的效果。 The effects of the present invention will be further verified below in conjunction with specific examples.
具体实施方式 Detailed ways
实施例1： Example 1:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸异丙酯的质量比为9：1，正硅酸四乙酯与钛酸异丙酯的用量摩尔比为1：2，氯化铝与钛酸异丙酯的用量摩尔比为1:10；其中：乙二醇的用量为2500ml/molTi，反应恒定温度为200℃，搅拌的速度为2000r/min；同时滴加少量的水促进水解，水的用量为250ml/molTi，而且水的pH值在8，滴加的时间在25min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to isopropyl titanate is 9:1, the molar ratio of tetraethyl orthosilicate to isopropyl titanate is 1:2, The molar ratio of aluminum chloride to isopropyl titanate is 1:10; among them, the amount of ethylene glycol is 2500ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 2000r/min; at the same time, a small amount of Water promotes hydrolysis, the amount of water is 250ml/molTi, and the pH value of water is 8, the time of dropping is within 25min, stirring, constant temperature; the prepared precipitate is washed with acetone to remove residual ethylene glycol, and finally the precipitate Vacuum drying at 70°C to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.04g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为90.68，色相b值1.0，特性粘度为0.722，羧基含量为13mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.04g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester has a hue L value of 90.68, a hue b value of 1.0, an intrinsic viscosity of 0.722 and a carboxyl content of 13 mol/t.
实施例2： Example 2:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸异丙酯的质量比为9：1，正硅酸四乙酯与钛酸异丙酯的用量摩尔比为1：2，氯化铝与钛酸异丙酯的用量摩尔比为1:10；其中：乙二醇的用量为2600ml/molTi，反应恒定温度为200℃，搅拌的速度为2500r/min；同时滴加少量的水促进水解，水的用量为260ml/molTi，而且水的pH值在8.5，滴加的时间在30min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to isopropyl titanate is 9:1, the molar ratio of tetraethyl orthosilicate to isopropyl titanate is 1:2, The molar ratio of aluminum chloride to isopropyl titanate is 1:10; among them, the amount of ethylene glycol is 2600ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 2500r/min; at the same time, a small amount of Water promotes hydrolysis, the amount of water is 260ml/molTi, and the pH value of water is 8.5, the time of dropping is within 30min, stirring, constant temperature; the prepared precipitate is washed with acetone to remove residual ethylene glycol, and finally the precipitate Vacuum drying at 70°C to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.05g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为91.68，色相b值1.2，特性粘度为0.712，羧基含量为12mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.05g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester has a hue L value of 91.68, a hue b value of 1.2, an intrinsic viscosity of 0.712 and a carboxyl content of 12 mol/t.
实施例3： Example 3:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸异丙酯的质量比为9：1，正硅酸四乙酯与钛酸异丙酯的用量摩尔比为1：2，氯化铝与钛酸异丙酯的用量摩尔比为1:10；其中：乙二醇的用量为2500ml/molTi，反应恒定温度为200℃，搅拌的速度为3000r/min；同时滴加少量的水促进水解，水的用量为260ml/molTi，而且水的pH值在8，滴加的时间在30min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to isopropyl titanate is 9:1, the molar ratio of tetraethyl orthosilicate to isopropyl titanate is 1:2, The molar ratio of aluminum chloride to isopropyl titanate is 1:10; among them: the amount of ethylene glycol is 2500ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 3000r/min; at the same time, a small amount of Water promotes hydrolysis, the consumption of water is 260ml/molTi, and the pH value of water is 8, and the time of dripping is within 30min, stirring, constant temperature; The prepared precipitation is washed with acetone, removes residual ethylene glycol, finally the precipitation Vacuum drying at 70°C to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.06g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为87.68，色相b值1.5，特性粘度为0.732，羧基含量为16mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.06g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester had a hue L value of 87.68, a hue b value of 1.5, an intrinsic viscosity of 0.732 and a carboxyl content of 16 mol/t.
实施例4： Example 4:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸异丙酯的质量比为8：1，正硅酸四乙酯与钛酸异丙酯的用量摩尔比为1：3，氯化铝与钛酸异丙酯的用量摩尔比为1:8；其中：乙二醇的用量为2500ml/molTi，反应恒定温度为200℃，搅拌的速度为2000r/min；同时滴加少量的水促进水解，水的用量为250ml/molTi，而且水的pH值在8，滴加的时间在25min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to isopropyl titanate is 8:1, the molar ratio of tetraethyl orthosilicate to isopropyl titanate is 1:3, The molar ratio of aluminum chloride to isopropyl titanate is 1:8; among them, the amount of ethylene glycol is 2500ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 2000r/min; at the same time, a small amount of Water promotes hydrolysis, the amount of water is 250ml/molTi, and the pH value of water is 8, the time of dropping is within 25min, stirring, constant temperature; the prepared precipitate is washed with acetone to remove residual ethylene glycol, and finally the precipitate Vacuum drying at 70°C to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.06g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为87.68，色相b值3.5，特性粘度为0.732，羧基含量为16mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.06g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester has a hue L value of 87.68, a hue b value of 3.5, an intrinsic viscosity of 0.732 and a carboxyl content of 16 mol/t.
实施例5： Example 5:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸异丙酯的质量比为10：1，正硅酸四乙酯与钛酸异丙酯的用量摩尔比为1.5：2，氯化铝与钛酸异丙酯的用量摩尔比为1:9；其中：乙二醇的用量为2600ml/molTi，反应恒定温度为200℃，搅拌的速度为3000r/min；同时滴加少量的水促进水解，水的用量为260ml/molTi，而且水的pH值在8.5，滴加的时间在30min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to isopropyl titanate is 10:1, the molar ratio of tetraethyl orthosilicate to isopropyl titanate is 1.5:2, The molar ratio of aluminum chloride to isopropyl titanate is 1:9; among them, the amount of ethylene glycol is 2600ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 3000r/min; at the same time, a small amount of Water promotes hydrolysis, the amount of water is 260ml/molTi, and the pH value of water is 8.5, the time of dropping is within 30min, stirring, constant temperature; the prepared precipitate is washed with acetone to remove residual ethylene glycol, and finally the precipitate Vacuum drying at 70°C to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.05g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为87.68，色相b值3.5，特性粘度为0.732，羧基含量为16mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.05g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester has a hue L value of 87.68, a hue b value of 3.5, an intrinsic viscosity of 0.732 and a carboxyl content of 16 mol/t.
实施例6： Embodiment 6:
低比表面积钛系聚酯催化剂的制备：先用恒温油浴将反应溶剂加热到某恒定温度，将钛酸异丙酯、三甲基磷酸酯、正硅酸四乙酯和氯化铝溶于乙二醇中，其中：三甲基磷酸酯加入的量与钛酸酯的质量比为9：2，正硅酸四乙酯与钛酸酯的用量摩尔比为1：2.5，氯化铝与钛酸酯的用量摩尔比为1.5:10；其中：乙二醇的用量为2500ml/molTi，反应恒定温度为200℃，搅拌的速度为3000r/min；同时滴加少量的水促进水解，水的用量为260ml/molTi，而且水的pH值在8，滴加的时间在25min内，搅拌，恒温；制得的沉淀用丙酮洗涤，除去残留的乙二醇，最后将沉淀在70℃下真空干燥，即得红色粉末催化剂； Preparation of low specific surface area titanium-based polyester catalyst: first heat the reaction solvent to a constant temperature with a constant temperature oil bath, dissolve isopropyl titanate, trimethyl phosphate, tetraethyl orthosilicate and aluminum chloride in In ethylene glycol, wherein: the mass ratio of trimethyl phosphate to titanate is 9:2, the molar ratio of tetraethyl orthosilicate to titanate is 1:2.5, aluminum chloride and titanate The molar ratio of the amount of titanate is 1.5:10; wherein: the amount of ethylene glycol is 2500ml/molTi, the constant reaction temperature is 200°C, and the stirring speed is 3000r/min; at the same time, a small amount of water is added dropwise to promote hydrolysis, and the The dosage is 260ml/molTi, and the pH value of the water is 8, the time of dropping is within 25min, stirring and constant temperature; the obtained precipitate is washed with acetone to remove the residual ethylene glycol, and finally the precipitate is vacuum-dried at 70°C , to obtain a red powder catalyst;
将2000g对苯二甲酸、1000g乙二醇与该催化剂0.04g在5L的不锈钢反应釜中进行聚酯反应。该过程在真空，270℃下进行。制得的聚酯色相L值为87.68，色相b值3.5，特性粘度为0.732，羧基含量为16mol/t。 2000g of terephthalic acid, 1000g of ethylene glycol and 0.04g of the catalyst were used for polyester reaction in a 5L stainless steel reactor. The process is carried out under vacuum at 270°C. The obtained polyester has a hue L value of 87.68, a hue b value of 3.5, an intrinsic viscosity of 0.732 and a carboxyl content of 16 mol/t.
结论： 通过以上的实施例数据可以表明，实施例1制得的聚酯色相L值为90.68，色相b值1.0，其L值较高同时b值也较低，为本发明的最佳方案；影响聚酯色相L值和色相b值的主要影响因素是低比表面积钛系聚酯催化剂的制备过程中三甲基磷酸酯加入的量与钛酸酯的质量比、正硅酸四乙酯与钛酸酯的用量摩尔比、氯化铝与钛酸酯的用量摩尔比，其他因素并不影响催化剂的活性，从而影响聚酯色相L值和色相b值。 Conclusion: Through the above example data, it can be shown that the polyester hue L value obtained in Example 1 is 90.68, the hue b value is 1.0, and its L value is higher while the b value is also lower, which is the best solution of the present invention; The main factors affecting the polyester hue L value and hue b value are the mass ratio of trimethyl phosphate to titanate, tetraethyl orthosilicate and The molar ratio of the amount of titanate, the molar ratio of the amount of aluminum chloride to titanate, and other factors do not affect the activity of the catalyst, thereby affecting the polyester hue L value and hue b value.
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