CN103242516A - Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer - Google Patents

Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer Download PDF

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CN103242516A
CN103242516A CN2013101953842A CN201310195384A CN103242516A CN 103242516 A CN103242516 A CN 103242516A CN 2013101953842 A CN2013101953842 A CN 2013101953842A CN 201310195384 A CN201310195384 A CN 201310195384A CN 103242516 A CN103242516 A CN 103242516A
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anhydride
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pvc
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蒋平平
张彩芹
苗红艳
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Jiangnan University
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Abstract

一种用作PVC增塑剂的甘油基聚酯的制备方法，属于化学合成技术领域。本发明以价格低廉的生物基甘油、非邻苯类二元酸（如六氢苯酐、己二酸等）为原料，在催化剂、封端剂、带水剂的共同作用下进行一步法合成，再经脱水缩聚、减压蒸馏等后处理过程制得聚二元酸甘油酯类增塑剂。产品的最终酸值在0.7-2mgKOH·g-1，酯化率高于97%，相对分子量在5000左右，分散系数在1.00-1.13之间，粘度适宜，物化性质稳定，按照一定配方加入到PVC中简练成PVC塑料试片，测试试片的应用性能如热稳定性、耐抽出性、拉伸性能等，试片的热稳定性良好，拉伸性能和耐迁移性优良。本发明原料价格低廉，制备工艺简单，能耗低，产品性能优异，具有良好的应用前景。

Figure 201310195384

The invention discloses a preparation method of glycerin-based polyester used as a PVC plasticizer, belonging to the technical field of chemical synthesis. The present invention uses low-cost bio-based glycerin and non-phthalic dibasic acids (such as hexahydrophthalic anhydride, adipic acid, etc.) After dehydration polycondensation, vacuum distillation and other post-treatment processes, polydibasic acid glyceride plasticizers are obtained. The final acid value of the product is 0.7-2mgKOH·g -1 , the esterification rate is higher than 97%, the relative molecular weight is about 5000, the dispersion coefficient is between 1.00-1.13, the viscosity is suitable, and the physical and chemical properties are stable. It is added to PVC according to a certain formula It is simplified into a PVC plastic test piece, and the application performance of the test piece is tested, such as thermal stability, extraction resistance, tensile performance, etc. The thermal stability of the test piece is good, and the tensile performance and migration resistance are excellent. The invention has low raw material price, simple preparation process, low energy consumption, excellent product performance and good application prospect.

Figure 201310195384

Description

A kind of preparation method who is used as the glyceryl polyester of PVC softening agent
Technical field
A kind of preparation method who is used as the glyceryl polyester of PVC softening agent belongs to chemosynthesis technical field.
Background technology
Softening agent is huge the reducing the high polymer material glass transition temperature and improve the additives for plastics of material plasticity of a kind of consumption, it adds the object kind and enriches, comprise plastics and rubber item, medical material, material of construction etc., play a different role in different interpolation objects with a kind of softening agent.At present, the softening agent that occupies main flow market is phthalate, large usage quantity as dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP).Yet, confirm after deliberation, after this type of softening agent enters human body, to the toxigenicity effect of a plurality of system of body, especially very big to women and children's harm.U.S. environment protection general bureau and European Parliament have limited multiple phthalic ester plasticizer in the application of environmental protection and health field, as sensitive materials such as toy for children, medicine equipment, food product pack.Therefore, the softening agent that synthetic nontoxic, environmental protection, anti-migration and plasticising performance are good is extremely urgent.
Plant oil based softening agent is to serve as the synthetic class non-toxic, environmental friendly softening agent in basis with biomass renewable resources vegetables oil, and the raw material of wherein producing plant oil based softening agent has three major types: natural fats and oils such as soybean oil, cottonseed wet goods; Glycerine; Processed the lipid acid (principal constituent is 18 carbon fatty acids) that obtains by natural fats and oils.Wherein, glycerine (being glycerol) mainly extensively is formed in the bodies of aminal and plant with glyceride form at occurring in nature, because it contains three more active hydroxyls and cheap environmental protection gains great popularity.
Polyester plasticizer is a kind of novel low relative molecular mass compound, and it is by two (many) units alcohol and the sour linear polymeric polymkeric substance that obtains by polycondensation of (many) units, is an important kind of softening agent.Compare with the softening agent of monomer molecule structure, it has, and transport property is little, high temperature resistant, the characteristics of anti-extraction, and outstanding low-temperature impact resistance, very high tearing toughness and anti-extraction ability are arranged in the PVC goods.Mainly be used as indoor and outdoors such as the interior goods of automobile, electric wire, the low temperature resistant equipment of refrigerator to low temperature or extract demanding functional plastic goods out, and the use field is increasingly extensive, be to develop a class special plasticiser faster, in the contradiction that mainly solves aspect the applied research between weather resistance and processibility, the low temperature properties.
Expect overcoming the drawback of conventional plasticizers thus, the advantages of plant oil based softening agent and polyester plasticizer is in the same place.Polyester plasticizer needs raw material to contain two carboxyls or two hydroxyls, can directly carry out the few of polyesterification reaction in plant oil based, need carry out a step organic synthesis earlier, and the glycerine in plant oil based contains three hydroxyls, and terminal hydroxy group has uncle's radical reaction characteristic.Make the glyceryl polyester plasticizer by this idea by glycerine, the product that obtains joins among the PVC according to certain prescription, and the plastics test piece empirical tests of terse one-tenth has thermostability preferably, higher resistance to migration energy and mechanical stretching performance.
Summary of the invention
The object of the invention has provided a kind of preparation method who is used as the glyceryl polyester of PVC softening agent, overcome that the conventional plasticizers molecular weight is little, performance is single, with shortcomings such as the PVC consistency is relatively poor, provide have high thermal stability, glyceryl polyester plasticizer that strong, the anti-transport property of anti-extractable is good and preparation method thereof.Product can be used in the field that can have relatively high expectations to the softening agent feature of environmental protection, resistance to migration.
Technical scheme of the present invention: a kind of preparation method who is used as the poly-diprotic acid glyceryl ester of PVC softening agent, earlier by glycerine and non-adjacent benzene class diprotic acid such as hexanodioic acid, sebacic acid, MALEIC ANHYDRIDE, HHPA or methyl hexahydrophthalic anhydride, containing catalyzer (as tetra-n-butyl titanate, tin protochloride, antimonous oxide etc.), lower molecular weight monohydroxy-alcohol end-capping reagent such as isooctyl alcohol or secondary octanol, carry out the reaction of single stage method chain polymerization in the reactor of lower boiling band aqua under the high temperature, slough small molecule monomer through vacuum distillation process, obtain poly-diprotic acid glyceryl ester softening agent.
The concrete operations step is as follows:
(1) polyreaction: in reactor, add glycerine; non-adjacent benzene class diprotic acid (acid anhydride); the end-capping reagent monohydroxy-alcohol; catalyzer and band aqua; the nitrogen atmosphere protection; wherein the mol ratio of glycerine and diprotic acid (acid anhydride) is 1.0:1.2-1.0:1.4; the mol ratio of END CAPPED GROUP monohydroxy-alcohol and dibasic acid anhydride is 0.5:1.0-1.0:1.0; catalyst consumption is the 1.0%-1.4% of dibasic acid anhydride and end-capping reagent total mass; slowly heat up under the nitrogen protection; the control maximum temperature is no more than 220 ℃; the system acid number for the treatment of no longer reduces stopped reaction constantly, cool to room temperature under the nitrogen protection.
Catalyzer is a kind of of metal complex catalyst tetra-n-butyl titanate, tin protochloride, antimonous oxide;
The band aqua is hexanaphthene.
(2) underpressure distillation: change vacuum distillation apparatus, excessive pure and mild band aqua and small molecules product are steamed, namely obtain poly-diprotic acid glyceryl ester.
The binary acid or anhydride, the adjacent benzene class of right and wrong and other do not contain the binary acid or anhydride of phenyl ring, select a kind of of hexanodioic acid, sebacic acid, MALEIC ANHYDRIDE, HHPA, methyl hexahydrophthalic anhydride for use.
The end-capping reagent monohydroxy-alcohol is selected a kind of of 2-Ethylhexyl Alcohol, secondary octanol for use.
Beneficial effect of the present invention:
1) have ester bond and hydroxyl in the molecular structure of product, have the characteristics of functionalization, product can play plasticization effect in the PVC product, and does not contain benzene ring structure, the product low toxic and environment-friendly.
2) glyceryl is that a kind of plant oil based and diprotic acid that contains three hydroxyls carries out polyesterification reaction, and the product polyester plasticizer is high temperature resistant, anti-transport property and anti-extractable are all better.
3) building-up process is simple, and energy consumption is low, and cost of material is cheap, meets green and cleans production technique.
Description of drawings
Fig. 1 is the infrared spectrogram of poly-two samples of HHPA glyceryl ester, 3510cm -1Be-charateristic avsorption band of OH 2966cm -1, 1160cm -1, 662cm -1Be the charateristic avsorption band of C=C, 1735cm -1It is the charateristic avsorption band of ester C=O.
Fig. 2 is the thermal stability analysis figure of PVC test piece.As seen from the figure, added the PVC test piece 1 of poly-HHPA glyceryl ester softening agent, 2 extension starting temperature is about 270 ℃, is higher than traditional plasticizer phthalic acid dioctyl ester (DOP), tributyl citrate (TBC), thermostability is stronger.
Fig. 3 is the mass loss rate of PVC test piece 100 ℃ of following different times in the gac of equal in quality.Can obviously find out, the PVC test piece that has added the glyceryl polyester under identical ambient conditions mass loss rate well below the test piece that has added DOP, and lower than the mass loss rate of the test piece of using DOP fully by the composite test piece of DOP and glyceryl polyester plasticizer, this has proved absolutely that this glyceryl polyester plasticizer resistance to migration is good.
Embodiment
Enumerate embodiment and comparative example below and further illustrate technology contents of the present invention, but interest field of the present invention is not only limited to the scope of embodiment.
Embodiment 1:
In the four-hole boiling flask of 250mL, add the glycerine of 0.25mol(92 * 0.25=23g) respectively; 0.35mol(154.16 * 0.35=54g) HHPA; 0.20mol(130.23 * 0.20=26.05g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 0.90g antimonous oxide; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h; the calculating of acid number is with reference to GB/T1668-2008; react no longer reduce to acid number till; stop heating, be cooled to room temperature under the logical nitrogen, change vacuum distillation apparatus; excessive pure and mild band aqua and small molecules product are steamed; treat to stop when absence of liquid is dripped heating, be cooled to room temperature under the decompression state, can obtain poly-HHPA glyceryl ester.The final acid number of product 1 is 1.78mg KOHg -1, esterification yield is 98.71%, and product color is light yellow for clarification, characterizes conclusive evidence through infrared test and is poly-HHPA glyceryl ester, and testing its molecular weight through gel chromatography is 4889, and dispersion coefficient is 1.01.
Embodiment 2:
In the four-hole boiling flask of 250mL, add 0.25mol glycerine respectively; 0.30mol(154.16 * 0.30=46.25g) HHPA; 0.2mol(26.05g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 0.95g positive four butyl esters of metatitanic acid; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h; react no longer reduce to acid number till; stop heating; be cooled to room temperature under the logical nitrogen; change vacuum distillation apparatus, excessive pure and mild band aqua and small molecules product are steamed, treat to stop when absence of liquid is dripped heating; be cooled to room temperature under the decompression state, can obtain poly-HHPA glyceryl ester.The final acid number of product 2 is 1.56mg KOHg -1, esterification yield is 99.21%, product color is light yellow for clarification, and characterize conclusive evidence through infrared test and be poly-HHPA glyceryl ester, the poly-HHPA glyceryl ester 1 among infared spectrum such as Fig. 1, testing its molecular weight through gel chromatography is 5039, dispersion coefficient is 1.02.
According to the PVC powder: softening agent: the mass ratio of thermo-stabilizer is that the prescription of 100:70:1 mixes three kinds of materials, place the terse PVC test piece 1 that makes on the twin-roll plastic mixing mill then, thermostability curve such as Fig. 2 of PVC test piece 1, resistance to migration energy curve such as Fig. 3, tensile property data such as table 1.
Embodiment 3:
In the four-hole boiling flask of 250mL, add 0.25mol glycerine respectively; 0.35mol(54g) HHPA; 0.2mol(26.05g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 1.10g tetra-n-butyl titanate; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h, till reaction treats that acid number no longer reduces, stop heating; be cooled to room temperature under the logical nitrogen; change vacuum distillation apparatus, excessive pure and mild band aqua and small molecules product are steamed, treat to stop when absence of liquid is dripped heating; be cooled to room temperature under the decompression state, can obtain poly-HHPA glyceryl ester.The final acid number of product 3 is 1.77mg KOHg -1, esterification yield is 99.51%, and product color is light yellow for clarification, and viscosity is moderate, characterizes conclusive evidence through infrared test and is poly-HHPA glyceryl ester, and testing its relative molecular weight through gel chromatography is 4869, dispersion coefficient is 1.00.
Embodiment 4:
In the four-hole boiling flask of 250mL, add 0.25mol glycerine respectively; 0.35mol(146.14 * 0.35=51.15g) hexanodioic acid; 0.3mol(39g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 0.90g tetra-n-butyl titanate; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h; reaction is treated that acid number no longer reduces and is stopped heating, is cooled to room temperature under the logical nitrogen, changes vacuum distillation apparatus; excessive pure and mild band aqua and small molecules product are steamed; treat to stop when absence of liquid is dripped heating, be cooled to room temperature under the decompression state, can obtain poly-hexanodioic acid glyceryl ester.The final acid number of product 4 is 0.97mg KOHg -1, esterification yield is 98.89%, and product color is light yellow for clarification, characterizes conclusive evidence through infrared test and is poly-hexanodioic acid glyceryl ester, and testing its relative molecular weight through gel chromatography is 4663, and dispersion coefficient is 1.01.
Embodiment 5:
In the four-hole boiling flask of 250mL, add 0.25mol glycerine respectively; 0.35mol(51.15g) hexanodioic acid; 0.2mol(26.05g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 0.87g tin protochloride; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h; the calculating of acid number is with reference to GB/T1668-2008; till reaction treated that acid number no longer reduces, esterification yield stopped heating greater than 99%; be cooled to room temperature under the logical nitrogen; change vacuum distillation apparatus, excessive pure and mild band aqua and small molecules product are steamed, treat to stop when absence of liquid is dripped heating; be cooled to room temperature under the decompression state, can obtain poly-hexanodioic acid glyceryl ester.The final acid number of product 5 is 0.58mgKOHg -1, esterification yield is 99.50%, and product color is light yellow for clarification, characterizes conclusive evidence through infrared test and is poly-hexanodioic acid glyceryl ester, and it is 4732 that gel chromatography is tested its relative molecular weight, and dispersion coefficient is 1.01.
Embodiment 6:
In the four-hole boiling flask of 250mL, add 0.25mol glycerine respectively; 0.35mol(54g) HHPA; 0.2mol(26.05g) 2-Ethylhexyl Alcohol; the 10mL hexanaphthene; 0.90g tetra-n-butyl titanate; logical nitrogen protection; begin to stir; slowly heat up; keeping temperature rise rate is 20 ℃/h; and top temperature is no more than 220 ℃; measure an acid number every 1h; the calculating of acid number is with reference to GB/T1668-2008; till reaction treats that acid number no longer reduces; stop heating, be cooled to room temperature under the logical nitrogen, change vacuum distillation apparatus; excessive pure and mild band aqua and small molecules product are steamed; treat to stop when absence of liquid is dripped heating, be cooled to room temperature under the decompression state, can obtain poly-HHPA glyceryl ester.The final acid number of product 6 is 0.85mg KOHg -1, esterification yield is 99.48%, product color is light yellow for clarification, and characterize conclusive evidence through infrared test and be poly-HHPA glyceryl ester, the poly-HHPA glyceryl ester 2 among infared spectrum such as Fig. 1, testing its molecular weight through gel chromatography is 5039, dispersion coefficient is 1.02.
According to the PVC powder: softening agent: the mass ratio of thermo-stabilizer is that the prescription of 100:70:1 mixes three kinds of materials, place the terse PVC test piece 2 that makes on the twin-roll plastic mixing mill then, thermostability curve such as Fig. 2 of PVC test piece 2, resistance to migration energy curve such as Fig. 3, tensile property data such as table 1.The toughness of PVC test piece that has added poly-HHPA glyceryl ester as can be seen is stronger, and tensile strength is better than conventional plasticizers, satisfactory mechanical property.
Table 1 has added the Elongation test data sheet of the terse PVC test piece of different softening agent.

Claims (3)

1.一种用作PVC增塑剂的聚二元酸甘油酯的制备方法，其特征在于先由甘油与二元酸或酐在含有催化剂、封端剂、带水剂的反应器中高温下进行一步法链式聚合反应，经过减压蒸馏过程脱去小分子单体，得到聚二元酸甘油酯增塑剂；操作步骤如下： 1. a kind of preparation method of the polydibasic acid glyceride as PVC plasticizer, it is characterized in that earlier by glycerin and dibasic acid or anhydride in the reactor that contains catalyzer, end-capping agent, band water agent under high temperature One-step chain polymerization reaction is carried out, and the small molecular monomers are removed through the process of vacuum distillation to obtain polyglyceride plasticizer; the operation steps are as follows: （1）聚合反应：在反应釜中加入甘油、非邻苯类二元酸或酐、封端剂一元醇、催化剂以及带水剂，氮气气氛保护，其中甘油与二元酸或酐的摩尔比为1.0:1.2-1.4，封端基一元醇与二元酸或酐的摩尔比为0.5-1.0:1.0，催化剂的用量为二元酸或酐及封端剂总质量的1.0%-1.4%，氮气保护下缓慢升温，控制最高反应温度不超过220℃，待体系酸值不再降低时停止反应，氮气保护下冷却到室温； (1) Polymerization reaction: Add glycerin, non-phthalic dibasic acid or anhydride, end-capping agent monohydric alcohol, catalyst and water-carrying agent to the reactor, and protect it under nitrogen atmosphere. The molar ratio of glycerol to dibasic acid or anhydride is: 1.0:1.2-1.4, the molar ratio of end-blocking monohydric alcohol to dibasic acid or anhydride is 0.5-1.0:1.0, and the amount of catalyst is 1.0%-1.4% of the total mass of dibasic acid or anhydride and end-capping agent, Slowly raise the temperature under the protection of nitrogen, control the maximum reaction temperature not to exceed 220°C, stop the reaction when the acid value of the system no longer decreases, and cool to room temperature under the protection of nitrogen; 催化剂为金属络合催化剂钛酸四正丁酯、氯化亚锡、三氧化二锑之一种； The catalyst is one of the metal complex catalysts tetra-n-butyl titanate, stannous chloride, and antimony trioxide; 带水剂为环己烷； The water-carrying agent is cyclohexane; （2）减压蒸馏：改换减压蒸馏装置，将过量的醇和带水剂以及小分子产物蒸出，即得到聚二元酸甘油酯。 (2) Vacuum distillation: Change the vacuum distillation device to distill off excess alcohol, water-carrying agent and small molecule products to obtain polyglycerol dibasic acid. 2.根据权利要求1所述的聚二元酸甘油酯的制备方法，其特征在于二元酸或酐，是非邻苯类及其他不含有苯环的二元酸或酐，选用己二酸、癸二酸、顺丁烯二酸酐、六氢苯酐、甲基六氢苯酐之一种。 2. the preparation method of polydibasic acid glyceride according to claim 1 is characterized in that dibasic acid or anhydride is non-o-phthalic and other dibasic acid or anhydride not containing benzene ring, selects adipic acid, One of sebacic acid, maleic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. 3.根据权利要求1所述的聚二元酸甘油酯的制备方法，其特征在于封端剂一元醇，选用2-乙基己醇、仲辛醇之一种。 3. the preparation method of polydibasic acid glyceride according to claim 1 is characterized in that end-capping agent monohydric alcohol, selects the one of 2-ethylhexanol, secondary octanol for use.
CN2013101953842A 2013-05-23 2013-05-23 Preparation method of glyceryl polyester used as PVC (Polyvinyl Chloride) plasticizer Pending CN103242516A (en)

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CN105555831A (en) * 2013-09-16 2016-05-04 巴斯夫欧洲公司 Polyester and use of polyester in lubricants
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CN106147066A (en) * 2015-03-27 2016-11-23 安徽瑞鑫自动化仪表有限公司 A kind of high-performance modified pvc material
CN104945783A (en) * 2015-07-24 2015-09-30 山东万图高分子材料有限公司 PVC polyester plasticizer as well as preparation method and application thereof
CN104945783B (en) * 2015-07-24 2016-08-24 山东万图高分子材料有限公司 A kind of PVC polyester plasticizer and its preparation method and application
CN107082980A (en) * 2017-05-09 2017-08-22 浙江兴宇汽车零部件有限公司 Low VOC polyvinyl chloride/PNBR thermoplastic elastic body sealing strip and preparation method thereof
CN114394896A (en) * 2022-01-17 2022-04-26 浙江镇洋发展股份有限公司 A kind of glyceryl ester plasticizer and preparation method thereof and non-toxic environment-friendly polyvinyl chloride
CN114956998A (en) * 2022-04-29 2022-08-30 江南大学 Preparation method of cyclohexyl terminated glutaric acid oligolactic acid ester plasticizer for PLA and PVC
CN114956998B (en) * 2022-04-29 2023-09-26 江南大学 Preparation method of cyclohexyl-ester-terminated glutaric acid oligomeric lactic acid ester plasticizer for PLA and PVC
CN115536820A (en) * 2022-09-28 2022-12-30 广东科云诚新材料有限公司 High-performance environment-friendly polyester plasticizer and preparation method thereof
CN115651230A (en) * 2022-11-07 2023-01-31 浙江恒百华化纤有限公司 PVC (polyvinyl chloride) coated polyester yarn and preparation method thereof
CN115651230B (en) * 2022-11-07 2023-11-14 浙江恒百华化纤有限公司 PVC (polyvinyl chloride) coated polyester yarn and preparation method thereof
CN116285147A (en) * 2022-12-26 2023-06-23 常州天龙医用新材料有限公司 A kind of plasticizer plasticized PVC material and preparation method thereof

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Application publication date: 20130814