CN103804669A - Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer - Google Patents
Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer Download PDFInfo
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Abstract
The invention discloses a method for preparing caster oil-based polyester serving as a PVC (Polyvinyl Chloride) plasticizer, belonging to the technical field of chemical synthesis. The method comprises the following steps: preparing caster oil-based dicarboxylic acid by reacting a down-stream product, namely, ricinoleic acid of low-price bio-based raw caster oil, dihydric anhydride and dihydric alcohol serving as raw materials in two steps: preparing caster oil-based dicarboxylic acid by using ricinoleic acid and dihydric anhydride, and carrying out a polyesterification reaction on the caster oil-based dicarboxylic acid and the dihydric alcohol in the coexistence of a catalyst and a water-carrying agent; and distilling under reduced pressure to obtain the caster oil-based polyester PVC plasticizer. A PVC plastic test piece is prepared by treating the caster oil-based polyester PVC plasticizer, PVC resin and a thermal stabilizer according to a certain formula through a solvent film casting method. The test piece is soft, and is equivalent to a PVC plastic piece plasticized by dioctyl phthalate (DOP) in the transparency under the same condition. The raw material is caster oil-based, recyclable, low in price and independent of petroleum, a preparation process is simple, and three wastes are not produced. The product is non-toxic, environment-friendly, resistant to migration, and superior in plasticizing performance, and has a good application prospect.
Description
Technical field
The preparation method who the present invention relates to a kind of castor oil-base polyester as PVC softening agent, belongs to chemosynthesis technical field.
Background technology
Softening agent is that one joins in macromolecular material (typically referring to resin, plastics or elastomerics), to improve their workability, plasticity-, flexible material.At present, the softening agent that occupies mainstream market is phthalate, large usage quantity as o-phthalic acid dibutyl ester (DOP), dibutyl phthalate (DBP).But, confirming after deliberation, this type of softening agent enters after human body, and the multiple systems of body are produced to toxic action, especially very large to women and children's harm.U.S. environment protection general bureau and European Parliament have limited the application of multiple phthalic ester plasticizer at 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, resistance to migration and plasticising performance are good is extremely urgent.
Plant oil based softening agent is that the raw material of wherein producing plant oil based softening agent has three major types: natural fats and oils is as Viscotrol C, soybean wet goods take biomass renewable resources vegetables oil as the synthetic class non-toxic, environmental friendly softening agent in basis; Glycerine; Processed the lipid acid (principal constituent is 18 carbon fatty acids) obtaining by natural fats and oils.Wherein, Viscotrol C is cheap, and raw material is easy to get, and has recyclability.
Polyester plasticizer is a kind of novel low relative molecular mass compound, and it is the linear polymeric polymkeric substance being obtained by polycondensation by two (many) first alcohol and the acid of two (many) units, is an important kind of softening agent.Compared with the softening agent of monomer molecule structure, it has, and transport property is little, high temperature resistant, the feature of resistance to extraction, has outstanding low-temperature impact resistance, very high tearing toughness and anti-extraction ability in PVC goods.It mainly requires high functional plastic goods as indoor and outdoors such as vapour vehicle interior article, electric wire, the low temperature resistant equipment of refrigerator to low temperature or extraction, and use field is increasingly extensive, to develop a class special plasticiser faster, in the contradiction mainly solving aspect applied research between weather resistance and processibility, low temperature properties.
Expect thus overcoming the drawback of conventional plasticizers, together with the advantages of plant oil based softening agent and polyester plasticizer.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 to first carry out a step organic synthesis.First prepare castor oil-base diprotic acid by cheap Viscotrol C derived product ricinolic acid and dibasic acid anhydride, then carry out polyesterification reaction by this diprotic acid and dibasic alcohol, make castor oil-base polyester softening agent through aftertreatments such as underpressure distillation.This polyester plasticizer product, polyvinyl chloride resin, thermo-stabilizer are prepared to the test piece of PVC plastics according to certain formula by solvent film casting method, test piece softness, the plastic sheet that under transparency and similarity condition prepared by DOP is suitable.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the castor oil-base polyester as PVC softening agent, it has overcome that conventional plasticizers molecular weight is little, performance is single, with the shortcoming such as PVC consistency is poor, provide to have that thermostability is strong, satisfactory mechanical property castor oil-base polyester as PVC softening agent that pliability is high and preparation method thereof.Product can be used in the field that the softening agent feature of environmental protection, PVC plastics flexibility are had relatively high expectations.
Technical scheme of the present invention, a kind of preparation method of the castor oil-base polyester as PVC softening agent, first prepare castor oil-base diprotic acid by ricinolic acid and dibasic acid anhydride, under catalyzer, acting in conjunction with aqua, carry out polyesterification reaction by this castor oil-base diprotic acid and dibasic alcohol again, make product through underpressure distillation processing; Concrete steps are as follows:
(1) preparation of castor oil-base diprotic acid: add ricinolic acid, dibasic acid anhydride and catalyzer in reactor, wherein the mol ratio of ricinolic acid and dibasic acid anhydride is 1:1, the add-on of catalyzer is 0.2% ~ 0.5% of ricinolic acid and dibasic acid anhydride total mass, temperature is controlled at 110 ℃ ~ 130 ℃, when reaction, measure reaction solution acid number, treating that acid number no longer reduces completes reaction, is cooled to room temperature, obtains castor oil-base diprotic acid;
Reaction equation is as follows:
(2) preparation of castor oil-base polyester softening agent head product: get castor oil-base diprotic acid, dibasic alcohol, catalyzer and band aqua prepared by step (1) and add in reactor, wherein castor oil-base diprotic acid: dibasic alcohol mol ratio is 1.0:1.2 ~ 1.0:1.5, the add-on of catalyzer is 1.0% ~ 3.0% of castor oil-base diprotic acid and dibasic alcohol total mass, and the add-on with aqua is 10% ~ 20% of castor oil-base diprotic acid and dibasic alcohol total mass; Above-mentioned raw materials is mixed, under nitrogen protection, slowly heat up, control maximum temperature and be no more than 210 ℃, stopped reaction in the time that system acid number no longer reduces, is cooled to room temperature under nitrogen protection, obtains castor oil-base polyester softening agent head product;
Reaction equation is as follows:
(3) underpressure distillation: get the underpressure distillation under 130 ℃ ~ 150 ℃, 0.05 ~ 0.1MPa of head product that step (2) obtains, do not have new cut to produce to still head place and do distillation end, continue to maintain under 0.05 ~ 0.1MPa pressure state and be cooled to room temperature, obtain the castor oil-base polyester of the finished product as PVC softening agent;
Described catalyzer is metal complex catalyst or homogeneous phase composite catalyst, is specially the one of tetra-n-butyl titanate, tin protochloride, antimonous oxide;
Described band aqua is hexanaphthene.
The described dibasic acid anhydride of step (1) is the one in hexahydrophthalic anhydride, MALEIC ANHYDRIDE, methyl hexahydrophthalic anhydride or Succinic anhydried.
The described dibasic alcohol of step (2) is: glycol ether, Triethylene glycol, BDO, methyl propanediol, ethylene glycol, the one in 1,3-PD.
Described product castor oil-base polyester PVC softening agent relative molecular weight is 4500 ~ 5500, and molecular weight distribution is 1.10 ~ 1.80.
Beneficial effect of the present invention:
(1) in the molecular structure of product, have ester bond and hydroxyl, have the feature of functionalization, product can play plasticization effect in PVC product, and does not contain benzene ring structure, product low toxic and environment-friendly.
(2) be prepared into plant oil based diprotic acid by ricinolic acid and acid anhydrides through a step organic synthesis, can carry out polyesterification reaction and make plant oil based polyester, reaction process is simply controlled.
(3) energy consumption is low, with low cost, and main raw material does not rely on oil, does not produce the three wastes, meets green and cleans production technique.
Accompanying drawing explanation
Fig. 1 is the P-RA-HHPA-DEG for preparing of embodiment 1 and the thermostability curve of DOP.
Fig. 2 is PVC plastics test piece by P-RA-HHPA-DEG and the DOP plasticising mass loss rate curve over time in the gac of 100 ℃.
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
A kind of preparation method of the castor oil-base polyester as PVC softening agent
(1) preparation of castor oil-base diprotic acid: adding concentration in 250mL there-necked flask is 87% ricinolic acid (RA, 0.25mol) 81.61g, hexahydrophthalic anhydride (HHPA, 0.25mol) 38.5g, to add tetra-n-butyl titanate 0.34g be catalyzer, temperature is controlled to 120 ℃, treat that acid number no longer reduces, be cooled to room temperature with for subsequent use.
(2) preparation of castor oil-base polyester softening agent head product: take above-mentioned castor oil-base diacid (0.086mol) 37.67g preparing, glycol ether (DEG, 0.12mol) 12.72g, 7.8g hexanaphthene, 0.95g tetra-n-butyl titanate add in reactor, logical nitrogen protection, start to stir, slowly heat up, and top temperature is no more than 210 ℃, measure an acid number every 1h, till reacting and no longer reducing to acid number, stop heating, under logical nitrogen protection, be cooled to room temperature;
(3) underpressure distillation: change vacuum distillation apparatus, at 140 ℃, under 0.08MPa, excessive alcohol and band aqua and small molecules product are steamed, in the time that dripping, absence of liquid stops heating, under decompression state, be cooled to room temperature, can obtain castor oil-base polyester plasticizer P-RA-HHPA-DEG.
The final acid number of product prepared by the present embodiment is 1.56mgKOHg
-1, esterification yield is 99.21%, and product color is light yellow for clarification, and testing its molecular weight through gel chromatography is 5043, and dispersion coefficient is 1.42, thermostability curve is as shown in Figure 1.
Can obviously be found out by Fig. 1, the thermostability of P-RA-HHPA-DEG is far away higher than DOP, and at 250 ℃ of same processing temperatures, DOP has decomposed more than half, but maintenance heat stability efficiently of P-RA-HHPA-DEG, illustrates that P-RA-HHPA-DEG is more suitable for industrial process applications process.
According to PVC powder: softening agent: the formula that the mass ratio of thermo-stabilizer is 100:70:1 is uniformly mixed three kinds of materials, make PVC test piece by solvent film casting method is terse, survey its resistance to migration curve as shown in Figure 2 according to standard with activated carbon method.
Can obviously be found out by Fig. 2, in 2h, the mass loss rate of two PVC plastics test pieces is suitable, this may be because there is residual the causing of oil on the PVC test piece surface of P-RA-HHPA-DEG plasticising, the mass loss rate of the PVC plastics test piece of P-RA-HHPA-DEG plasticising after 2h is well below the plastics test piece of DOP plasticising, and loss slowly, illustrates that the plasticizer P-RA-HHPA-DEG preparing according to method provided by the present invention shows excellent resistance to migration.
Embodiment 2
A kind of preparation method of the castor oil-base polyester as PVC softening agent
(1) preparation of castor oil-base diprotic acid: adding concentration in 250mL there-necked flask is 87% ricinolic acid (RA, 0.25mol) 81.61g, MALEIC ANHYDRIDE (MA, 0.25mol) 24.5g, to add antimonous oxide 0.34g be catalyzer, temperature is controlled to 110 ℃, treat that acid number no longer reduces, be cooled to room temperature with for subsequent use.
(2) preparation of castor oil-base polyester softening agent head product: take above-mentioned castor oil-base diacid (0.1mol) 38.2g preparing, Triethylene glycol (TEG, 0.12mol) 18g, 8.4g hexanaphthene, 0.75g antimonous oxide add in reactor, logical nitrogen protection, start to stir, slowly heat up, and top temperature is no more than 210 ℃, measure an acid number every 1h, till reacting and no longer reducing to acid number, stop heating, under logical nitrogen protection, be cooled to room temperature;
(3) underpressure distillation: change vacuum distillation apparatus, at 140 ℃, under 0.08MPa, excessive alcohol and band aqua and small molecules product are steamed, in the time that dripping, absence of liquid stops heating, under decompression state, be cooled to room temperature, can obtain castor oil-base polyester plasticizer P-RA-MA-TEG.
The final acid number of product 2 is 2.12mgKOHg
-1, esterification yield is 99.32%, and product color is light yellow for clarification, and testing its molecular weight through gel chromatography is 5276, and dispersion coefficient is 1.51.According to PVC powder: softening agent: the formula that the mass ratio of thermo-stabilizer is 100:70:1 is uniformly mixed three kinds of materials, with tetrahydrofuran (THF) as solvent, make PVC test piece by solvent film casting method is terse, test piece softness, the plastic sheet that under transparency and similarity condition prepared by DOP is suitable, and resistance to migration is good.
Embodiment 3
A kind of preparation method of the castor oil-base polyester as PVC softening agent
(1) preparation of castor oil-base diprotic acid: adding concentration in 250mL there-necked flask is 87% ricinolic acid (RA, 0.25mol) 81.61g, hexahydrophthalic anhydride (HHPA, 0.25mol) 38.5g, to add tetra-n-butyl titanate 0.34g be catalyzer, temperature is controlled to 120 ℃, treat that acid number no longer reduces, be cooled to room temperature with for subsequent use.
(2) preparation of castor oil-base polyester softening agent head product: take above-mentioned castor oil-base diacid (0.086mol) 37.88g preparing, BDO (BDO, 0.12mol) 10.8g, 8.7g hexanaphthene, 0.55g tetra-n-butyl titanate add in reactor, and logical nitrogen protection starts to stir, slowly heat up, and top temperature is no more than 210 ℃, till 1h measures an acid number, reacts and no longer reduce to acid number, stop heating, under logical nitrogen protection, be cooled to room temperature;
(3) underpressure distillation: change vacuum distillation apparatus, at 140 ℃, under 0.07MPa, excessive alcohol and band aqua and small molecules product are steamed, in the time that dripping, absence of liquid stops heating, under decompression state, be cooled to room temperature, can obtain castor oil-base polyester plasticizer P-RA-HHPA-BDO.
The final acid number of product 3 is 1.64mgKOHg
-1, esterification yield is 99.29%, and product color is light yellow for clarification, and testing its molecular weight through gel chromatography is 5235, and dispersion coefficient is 1.60.According to PVC powder: softening agent: the formula that the mass ratio of thermo-stabilizer is 100:70:1 is uniformly mixed three kinds of materials, with tetrahydrofuran (THF) as solvent, make PVC test piece by solvent film casting method is terse, test piece softness, the mechanical property of product 1,2,3 is as shown in table 1.
Table 1 is the mechanical performance data of product 1,2,3, and from tensile strength, tensile strength and the DOP of synthetic softening agent are suitable, but elongation at break is far longer than DOP, illustrates that the synthetic softening agent of this method can make PVC pliability increase.
The data analysis of table 1 PVC test piece tensile property
。
Claims (4)
1. the preparation method as the castor oil-base polyester of PVC softening agent, it is characterized in that: first prepare castor oil-base diprotic acid by ricinolic acid and dibasic acid anhydride, under catalyzer, acting in conjunction with aqua, carry out polyesterification reaction by this castor oil-base diprotic acid and dibasic alcohol again, make product through underpressure distillation processing; Concrete steps are as follows:
(1) preparation of castor oil-base diprotic acid: add ricinolic acid, dibasic acid anhydride and catalyzer in reactor, wherein the mol ratio of ricinolic acid and dibasic acid anhydride is 1:1, the add-on of catalyzer is 0.2% ~ 0.5% of ricinolic acid and dibasic acid anhydride total mass, temperature is controlled at 110 ℃ ~ 130 ℃, when reaction, measure reaction solution acid number, treating that acid number no longer reduces completes reaction, is cooled to room temperature, obtains castor oil-base diprotic acid;
(2) preparation of castor oil-base polyester softening agent head product: get castor oil-base diprotic acid, dibasic alcohol, catalyzer and band aqua prepared by step (1) and add in reactor, wherein castor oil-base diprotic acid: dibasic alcohol mol ratio is 1.0:1.2 ~ 1.0:1.5, the add-on of catalyzer is 1.0% ~ 3.0% of castor oil-base diprotic acid and dibasic alcohol total mass, and the add-on with aqua is 10% ~ 20% of castor oil-base diprotic acid and dibasic alcohol total mass; Above-mentioned raw materials is mixed, under nitrogen protection, slowly heat up, control maximum temperature and be no more than 210 ℃, stopped reaction in the time that system acid number no longer reduces, is cooled to room temperature under nitrogen protection, obtains castor oil-base polyester softening agent head product;
(3) underpressure distillation: get the underpressure distillation under 130 ℃ ~ 150 ℃, 0.05 ~ 0.1MPa of head product that step (2) obtains, distillation finishes, continue to maintain under 0.05 ~ 0.1MPa pressure state and be cooled to room temperature, obtain the castor oil-base polyester of the finished product as PVC softening agent;
Described catalyzer is the one of tetra-n-butyl titanate, tin protochloride, antimonous oxide;
Described band aqua is hexanaphthene.
2. the preparation method who is used as according to claim 1 the castor oil-base polyester of PVC softening agent, is characterized in that: the described dibasic acid anhydride of step (1) is the one in hexahydrophthalic anhydride, MALEIC ANHYDRIDE, methyl hexahydrophthalic anhydride or Succinic anhydried.
3. the preparation method who is used as according to claim 1 the castor oil-base polyester of PVC softening agent, is characterized in that: the described dibasic alcohol of step (2) is: glycol ether, Triethylene glycol, BDO, methyl propanediol, ethylene glycol, the one in 1,3-PD.
4. the preparation method who is used as according to claim 1 the castor oil-base polyester of PVC softening agent, is characterized in that: described product is used as the castor oil-base polyester relative molecular weight of PVC softening agent 4500 ~ 5500, and molecular weight distribution is 1.10 ~ 1.80.
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| CN105255061A (en) * | 2015-11-16 | 2016-01-20 | 广东达华节水科技股份有限公司 | Environment-friendly soft PVC plasticizer |
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| CN107141460A (en) * | 2017-06-12 | 2017-09-08 | 浙江大学 | The synthetic method of one vegetable oil based thermoplastic polyester |
| CN108410092A (en) * | 2018-04-10 | 2018-08-17 | 朱文杰 | A kind of preparation method of polyvinyl-chloride use plasticizer |
| CN109867930A (en) * | 2019-02-20 | 2019-06-11 | 朱海鹏 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
| CN109912788A (en) * | 2019-02-27 | 2019-06-21 | 青岛科技大学 | A kind of environment-friendly plasticizer preparation method |
| CN109912788B (en) * | 2019-02-27 | 2021-03-02 | 青岛科技大学 | Preparation method of environment-friendly plasticizer |
| CN112661944A (en) * | 2020-12-30 | 2021-04-16 | 河南天宁新材料科技有限公司 | Polyester plasticizer and preparation method thereof |
| CN113402824A (en) * | 2021-06-24 | 2021-09-17 | 广东冠盛新材料有限公司 | Biodegradable PVC plastic and preparation method and application thereof |
| CN116589917A (en) * | 2023-06-13 | 2023-08-15 | 广州邦士度眼镜有限公司 | Cold-resistant mirror coating and preparation process thereof |
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