CN104987497A - A method for removing acid value in polyester polyol through column - Google Patents
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- CN104987497A CN104987497A CN201510425929.3A CN201510425929A CN104987497A CN 104987497 A CN104987497 A CN 104987497A CN 201510425929 A CN201510425929 A CN 201510425929A CN 104987497 A CN104987497 A CN 104987497A
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- 239000002253 acid Substances 0.000 title claims abstract description 34
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims abstract 2
- 230000008018 melting Effects 0.000 claims abstract 2
- 238000010025 steaming Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 150000002009 diols Chemical class 0.000 abstract description 9
- 229920005862 polyol Polymers 0.000 abstract description 6
- 150000003077 polyols Chemical class 0.000 abstract description 6
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及一种过柱去除聚酯多元醇中酸值的方法，把有机二元羧酸（酸酐或酯）与多元醇（包括二醇）加入反应器中熔融，通入氮气，于150℃左右反应生成水，逐步蒸出反应生成水，随水分的蒸出，釜内温度逐渐升高，并在过程中测定酸值，在170～230℃下，当酸值小于30mgKOH/g时，加入15～100ppm有机催化剂，并开始抽真空除去反应生成水和低分子量聚酯多元醇，使酸值小于2mgKOH/g,然后降温至80-100℃，以一定的流速通过碱性柱，得到酸值小于0.5mgKOH/g的聚酯多元醇，本发明的聚酯多元醇酸值去除工艺简单、成本低廉，市场前景好。The invention relates to a method for removing the acid value of polyester polyols through a column. Organic dicarboxylic acids (anhydrides or esters) and polyols (including diols) are added to a reactor for melting, and nitrogen gas is introduced into the reactor at 150°C. Left and right react to generate water, and gradually distill out the reaction to generate water. With the steaming of water, the temperature in the kettle gradually increases, and the acid value is measured during the process. At 170-230°C, when the acid value is less than 30mgKOH/g, add 15-100ppm organic catalyst, and start vacuuming to remove the reaction-generated water and low-molecular-weight polyester polyol, so that the acid value is less than 2mgKOH/g, then cool down to 80-100°C, and pass through the basic column at a certain flow rate to obtain the acid value For polyester polyols less than 0.5 mgKOH/g, the polyester polyol acid value removal process of the present invention is simple, low in cost, and has good market prospects.
Description
技术领域 technical field
本发明属于合成树脂领域，具体涉及到一种过柱去除聚酯多元醇中酸值的方法。 The invention belongs to the field of synthetic resins, and in particular relates to a method for removing the acid value of polyester polyols through a column.
背景技术 Background technique
聚酯多元醇通常是由有机二元羧酸（酸酐或酯）与多元醇（包括二醇）缩合（或酯交换）或由内酯与多元醇聚合而成，主要用于聚氨酯树脂的合成原料。其制备过程一般都采用间歇法生产：即生产时首先把有机二元羧酸（酸酐或酯）与多元醇（包括二醇）加入反应器中熔融，通入氮气，于150℃左右反应生成水，逐步蒸出，釜内生成低聚酯混合物(低分子量聚酯多元醇）。随水分的蒸出，釜内温度逐渐升高，在170～230℃下，真空度逐步降到500Pa，将过量的二元醇和少量副反应产物(低分子聚酯、醛及酮)与反应生成的残留水一起蒸出。对于聚酯多元醇比较重要的几个指标是羟值、酸值、水分、粘度、分子量、密度以及色度等，其中酸值对下一步聚氨酯的合成有很大的影响，所以通常要求聚酯多元醇的酸值小于0.5mgKOH/g，要达到这个酸值要求，一般采用的方法是在反应后期加入过量的低分子二元醇或最后加入KOH、NaOH水溶液中和，但在反应后期加入过量的低分子二元醇使残余酸性物质完全反应，需使用大量的低分子二元醇，增加的回收过量低分子二元醇能耗及损失；而最后加入KOH、NaOH水溶液中和除酸值，则容易使聚酯多元醇产生皂化现象。 Polyester polyols are usually formed by condensation (or transesterification) of organic dicarboxylic acids (anhydrides or esters) and polyols (including diols) or by polymerization of lactones and polyols, and are mainly used as raw materials for the synthesis of polyurethane resins . The preparation process is generally produced by batch method: that is, the organic dicarboxylic acid (anhydride or ester) and polyol (including diol) are first added to the reactor to melt, and nitrogen is introduced to react at about 150 ° C to form water. , gradually evaporated, and a low-polyester mixture (low-molecular-weight polyester polyol) was generated in the kettle. With the evaporation of water, the temperature in the kettle gradually rises, and at 170-230°C, the vacuum degree is gradually reduced to 500Pa, and the excess diol and a small amount of by-reaction products (low molecular weight polyester, aldehyde and ketone) are reacted with the reaction product The residual water was evaporated together. Several important indicators for polyester polyols are hydroxyl value, acid value, moisture, viscosity, molecular weight, density and chroma, etc. Among them, the acid value has a great influence on the synthesis of polyurethane in the next step, so polyester polyols are usually required The acid value of polyols is less than 0.5mgKOH/g. To meet this acid value requirement, the general method is to add excess low-molecular-weight diols in the late stage of the reaction or finally add KOH and NaOH aqueous solution to neutralize, but in the late stage of the reaction, add excessive The low-molecular-weight diols can completely react the residual acidic substances, so a large amount of low-molecular-weight diols needs to be used, which will increase the energy consumption and loss of recovering excess low-molecular-weight diols; and finally add KOH and NaOH aqueous solution to neutralize the acid removal value, It is easy to cause saponification of polyester polyol.
发明内容 Contents of the invention
为克服现行聚酯多元醇酸值达标所采取的工艺做法存在的问题，本发明采用过碱性柱除去聚酯多元醇的酸值。 In order to overcome the problems existing in the current process of polyester polyol acid value reaching the standard, the present invention adopts an overbasic column to remove the acid value of polyester polyol.
本发明的技术方案为：Technical scheme of the present invention is:
1、碱性柱的制备： 1. Preparation of basic column:
在直径为30-50cm、高度为1.0m的不锈钢柱中装入碱性物质，装柱高度为0.5-0.8m，备用。 Load alkaline substances into a stainless steel column with a diameter of 30-50cm and a height of 1.0m, and the height of the column is 0.5-0.8m, and set aside.
2、聚酯多元醇的合成： 2. Synthesis of polyester polyols:
把有机二元羧酸（酸酐或酯）与多元醇（包括二醇）加入反应器中熔融，通入氮气，于150℃左右反应生成水，逐步蒸出反应生成水。随水分的蒸出，釜内温度逐渐升高，并在过程中测定酸值。在170～230℃下，当酸值小于30mgKOH/g时，加入15～100ppm有机催化剂，并开始抽真空除去反应生成水和低分子量聚酯多元醇，使酸值小于2mgKOH/g,然后降温至80-100℃，以一定的流速通过碱性柱，得到酸值小于0.5mgKOH/g的聚酯多元醇。 Add organic dicarboxylic acid (acid anhydride or ester) and polyol (including diol) into the reactor to melt, pass nitrogen gas, react at about 150°C to form water, and gradually distill out the reaction to form water. With the evaporation of water, the temperature in the kettle gradually increased, and the acid value was measured during the process. At 170-230°C, when the acid value is less than 30mgKOH/g, add 15-100ppm organic catalyst, and start vacuuming to remove the reaction water and low molecular weight polyester polyol, so that the acid value is less than 2mgKOH/g, and then cool down to 80-100°C, pass through the basic column at a certain flow rate to obtain polyester polyols with an acid value of less than 0.5 mgKOH/g.
本发明所述的碱性物质为KOH、NaOH、甲醇钠、乙醇钠、丙醇钠、丁醇钠中的一种或几种。 The alkaline substance in the present invention is one or more of KOH, NaOH, sodium methoxide, sodium ethoxide, sodium propoxide and sodium butoxide.
本发明所述的聚酯多元醇通过碱性柱的流速为5g-10kg/min。 The flow rate of the polyester polyol in the present invention through the basic column is 5g-10kg/min.
本发明的有益结果是聚酯多元醇的酸值去除工艺简单、成本低廉。 The beneficial result of the invention is that the acid value removal process of the polyester polyol is simple and the cost is low.
具体实施方式 Detailed ways
以下下是本发明的几个具体实施例，进一步说明本发明，但是本发明不仅限于此。 Below are several specific embodiments of the present invention, further illustrate the present invention, but the present invention is not limited thereto.
实施例1Example 1
把对苯二甲酸与乙二醇加入反应器中熔融，通入氮气，于150℃反应生成水，逐步蒸出反应生成水。随水分的蒸出，釜内温度逐渐升高至190℃，测定酸值为25mgKOH/g时，加入80ppm钛酸四异丙酯催化剂，并开始抽真空除去反应生成水和低分子量聚酯多元醇，测定酸值为1.5mgKOH/g,然后降温至90℃，以10g/min流速通过直径为50cm、高度为1.0m的装有高度为0.8m的KOH不锈钢柱碱性柱，得到酸值为0.45mgKOH/g的聚酯多元醇。 Put terephthalic acid and ethylene glycol into the reactor to melt, pass through nitrogen, react at 150°C to generate water, and gradually distill out the reaction to generate water. With the evaporation of water, the temperature in the kettle gradually increased to 190°C. When the acid value was measured to be 25mgKOH/g, 80ppm tetraisopropyl titanate catalyst was added, and vacuum was started to remove the reaction-generated water and low-molecular-weight polyester polyol. , the acid value was measured to be 1.5mgKOH/g, and then the temperature was lowered to 90°C, and the basic column with a diameter of 50cm and a height of 1.0m equipped with a KOH stainless steel column with a height of 0.8m was passed through at a flow rate of 10g/min, and the acid value was obtained as 0.45 mgKOH/g of polyester polyol.
实施例2Example 2
把己二酸与丁二醇加入反应器中熔融，通入氮气，于155-158℃反应生成水，逐步蒸出反应生成水。随水分的蒸出，釜内温度逐渐升高至200℃，测定酸值为27mgKOH/g时，加入70ppm钛酸四丁酯催化剂，并开始抽真空除去反应生成水和低分子量聚酯多元醇，测定酸值为1.9mgKOH/g,然后降温至100℃，以8kg/min流速通过直径为40cm、高度为1.0m的装有高度为0.9m的乙醇钠不锈钢柱碱性柱，得到酸值为0.41mgKOH/g的聚酯多元醇。 Add adipic acid and butanediol into the reactor to melt, feed nitrogen, react at 155-158°C to generate water, and gradually distill out the reaction to generate water. With the evaporation of water, the temperature in the kettle gradually increased to 200°C. When the acid value was measured to be 27mgKOH/g, 70ppm tetrabutyl titanate catalyst was added, and vacuum was started to remove the reaction-generated water and low-molecular-weight polyester polyol. Measure the acid value to 1.9mgKOH/g, then lower the temperature to 100°C, pass through a 40cm-diameter, 1.0m-height alkaline column equipped with a sodium ethoxide stainless steel column with a height of 0.9m at a flow rate of 8kg/min, and the acid value is 0.41 mgKOH/g of polyester polyol.
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| CN111458453A (en) * | 2020-05-12 | 2020-07-28 | 万华化学集团股份有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
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| CN111458453A (en) * | 2020-05-12 | 2020-07-28 | 万华化学集团股份有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
| CN111458453B (en) * | 2020-05-12 | 2022-07-12 | 万华化学(四川)有限公司 | Method for testing hydroxyl value in lactide-containing polylactic acid and application thereof |
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Application publication date: 20151021 |