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 PDFInfo
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Abstract
The invention discloses a preparation method of glyceryl polyester used as a PVC (Polyvinyl Chloride) plasticizer and belongs to the technical field of chemical synthesis. The preparation method comprises the following steps of: synthesizing by a one-step process under the combined action of a catalyst, an end-capping reagent and a water-carrying agent by using cheap bio-based glycerol, non-orthophthalic binary acid (for example hexahydrophthalic anhydride, adipic acid or the like) as the materials; and carrying out the post-treatment processes including dehydration poly-condensation, reduced pressure distillation and the like to obtain the poly-binary acid glyceride plasticizer. The glyceride plasticizer has a final acid value of 0.7mgKOH.g<-1>-2mgKOH.g<-1>, an esterification rate higher than 97%, relative molecular weight of about 5000, a dispersion coefficient of 1.00-1.13, appropriate viscosity and stable physical and chemical characteristics; the glyceride plasticizer is added to the PVC according to a certain formula to be refined into a PVC plastic test block, so that application performances including heat stability, drawing resistance, tensile performance and the like of the test block are tested; and the test block has good heat stability, tensile performance and excellent mobility resistance. The preparation method of the glyceryl polyester used as the PVC plasticizer is low in material price, simple in preparation process, low in energy consumption, excellent in product performance and good in application prospect.
Description
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. preparation method as the poly-diprotic acid glyceryl ester of PVC softening agent, it is characterized in that in the reactor that contains catalyzer, end-capping reagent, band aqua, carrying out the reaction of single stage method chain polymerization under the high temperature by glycerine and binary acid or anhydride earlier, slough small molecule monomer through vacuum distillation process, obtain poly-diprotic acid glyceryl ester softening agent; Operation steps is as follows:
(1) polyreaction: in reactor, add glycerine, non-adjacent benzene class binary acid or anhydride, end-capping reagent monohydroxy-alcohol, catalyzer and band aqua, the nitrogen atmosphere protection, wherein the mol ratio of glycerine and binary acid or anhydride is 1.0:1.2-1.4, the mol ratio of END CAPPED GROUP monohydroxy-alcohol and binary acid or anhydride is 0.5-1.0:1.0, catalyst consumption is the 1.0%-1.4% of binary acid or anhydride and end-capping reagent total mass, slowly heat up under the nitrogen protection, the control maximum temperature is no more than 220 ℃, stopped reaction when the system acid number for the treatment of no longer reduces, 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.
2. the preparation method of poly-diprotic acid glyceryl ester according to claim 1, it is characterized in that 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.
3. the preparation method of poly-diprotic acid glyceryl ester according to claim 1 is characterized in that the end-capping reagent monohydroxy-alcohol, selects a kind of of 2-Ethylhexyl Alcohol, secondary octanol for use.
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| 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 |
| CN105555831A (en) * | 2013-09-16 | 2016-05-04 | 巴斯夫欧洲公司 | Polyester and use of polyester in lubricants |
| 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 |
| 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 | Glyceryl ester plasticizer, preparation method thereof and nontoxic 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 |
| 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 |
| CN116285147A (en) * | 2022-12-26 | 2023-06-23 | 常州天龙医用新材料有限公司 | Plasticizer plasticized PVC material and preparation method thereof |
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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 |
| US10150928B2 (en) | 2013-09-16 | 2018-12-11 | Basf Se | Polyester and use of polyester in lubricants |
| 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 |
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| 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 | Glyceryl ester plasticizer, preparation method thereof and nontoxic 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 | Plasticizer plasticized PVC material and preparation method thereof |
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Application publication date: 20130814 |