CN111499925B - Plasticizer compound, preparation method and PVC composite material containing plasticizer compound - Google Patents
Plasticizer compound, preparation method and PVC composite material containing plasticizer compound Download PDFInfo
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- CN111499925B CN111499925B CN202010433664.2A CN202010433664A CN111499925B CN 111499925 B CN111499925 B CN 111499925B CN 202010433664 A CN202010433664 A CN 202010433664A CN 111499925 B CN111499925 B CN 111499925B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention relates to the technical field related to plasticizers, and particularly provides a plasticizer composite, a preparation method and a PVC composite material containing the plasticizer composite. The first aspect of the invention provides a plasticizer compound, the preparation raw materials comprise diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid; wherein the alcohol comprises n-decanol. The invention mainly provides a light-color plasticizer, which improves the processability of the plasticizer and a PVC (polyvinyl chloride) base material, improves the temperature resistance of a product obtained by using the plasticizer, reduces the haze and the taste of a composite material, and reduces the discharge amount of VOC (volatile organic compound) gas.
Description
Technical Field
The invention relates to the technical field related to plasticizers, and particularly provides a plasticizer compound, a preparation method and a PVC composite material containing the plasticizer compound.
Background
With the improvement of the quality of life, the internal control quality of the automobile is more and more strict. Odor and organic volatilization are just one of the most complaints of automobile customers. The plasticizer greatly contributes to odor and organic volatilization as one of main raw materials of the automotive upholstery, so the use of the high-quality plasticizer is key to low odor and low volatilization.
In addition, in addition to the odor requirement, the manufacturing customers of the automotive interior materials also put forward higher performance requirements, such as that the plasticizer is more beneficial to the preparation of the materials in the using process, the excessive requirement on the conditions in the preparation process is reduced, and the color requirement of the plasticizer is also improved, so that the light-color substances are more required to be adopted, the aesthetic degree of the obtained materials is improved, and the high-temperature and low-temperature resistance of the materials containing the plasticizer is also higher, so that the temperature resistance of the automotive interior materials is improved; however, the plasticizers of CN105237803, CN108218700, CN109503371, etc. which have been applied at present have some defects in the color of the plasticizer, the processing conditions of the composite material containing the plasticizer, and the temperature resistance of the product.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a plasticizer composite, which comprises raw materials for preparation, including diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid; wherein the alcohol comprises n-decanol.
As a preferred technical scheme of the invention, the alcohols also comprise dodecanol and isodecanol.
As a preferable technical scheme of the invention, the weight ratio of the dodecanol, the n-decanol and the iso-decanol is 1: (1.2-1.4): (0.8 to 1.2); preferably 1: (1.25-1.35): (0.95-1.1).
As a preferred technical scheme of the invention, the diacid anhydride substances are selected from any one or a combination of more of glutaric anhydride, oxalic anhydride, succinic anhydride and phthalic anhydride; phthalic anhydride is preferred.
According to a preferable technical scheme of the invention, the weight ratio of the alcohol substance to the diacid anhydride substance is (2.5-3.5): 1.
in a preferred embodiment of the present invention, the purity of the diacid anhydride is 99.5% or higher.
As a preferred technical scheme of the invention, the carbonyl value of the decanol is less than 40 mg/kg; preferably, the carbonyl number of the decanol is less than 20 mg/kg; further preferably, the carbonyl value of n-decanol is less than 10 mg/kg.
The second aspect of the invention provides a preparation method of the plasticizer compound, which comprises four steps of esterification reaction, refining, pressure filtration and molecular distillation.
As a preferred technical solution of the present invention, the method for preparing the plasticizer composite comprises the steps of: (1) esterification reaction: adding alcohols and diacid anhydrides into a reaction kettle, adding a catalyst, starting to pump air into the reaction kettle when the temperature is raised to 220 +/-10 ℃ to ensure that the kettle is in a negative pressure state, and continuing to start a vacuum pump to carry out negative pressure and dealcoholization when the esterification acid value is less than or equal to 0.1 mgKOH/g;
(2) refining: cooling the substances in the step (1), adding alkaline water for neutralization, heating and stripping while raising the temperature after neutralization, raising the temperature to 215 +/-10 ℃, keeping stripping for 2.5-4h, and ensuring that the central control index is qualified; preparing to enter a filter pressing operation;
(3) and (3) filter pressing: preserving the heat of the substances in the step (2) for 0.5h, then adding a filter aid for refining and stirring, and entering a molecular distillation stage after indexes are qualified after filter pressing;
(4) molecular distillation: subjecting the substance obtained in step (3) to molecular distillationWherein the vacuum degree is less than or equal to 100pa, so that the inlet temperature of the material is kept at 190 +/-10 ℃, and the sample injection amount is 0.6-1.0 m3/h。
In a third aspect, the invention provides a PVC composite for automotive trim comprising a PVC base material and the plasticizer composite.
Compared with the prior art, the plasticizer provided by the invention has the following beneficial effects:
(1) the invention adopts the n-decanol with low carbonyl value as the raw material for preparing the plasticizer, effectively reduces the color depth of the obtained plasticizer, and is beneficial to the multi-field use of the PVC material containing the plasticizer;
(2) the invention adopts the n-decanol, the iso-decanol and the dodecanol as the preparation raw materials of the plasticizer in a specific proportion, which is beneficial to the processing and preparation of the obtained plasticizer and PVC material;
(3) according to the invention, phthalic anhydride, n-decanol, isodecanol and dodecanol are used as the preparation raw materials of the plasticizer in a specific ratio, so that the improvement of the temperature resistance of the obtained PVC composite material is facilitated, the haze is further reduced, the discharge amount of VOC gas is reduced, and the taste of the composite material is reduced.
Detailed Description
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The invention mainly provides a light-color plasticizer, which improves the processability of the plasticizer and a PVC (polyvinyl chloride) base material, improves the temperature resistance of a product obtained by using the plasticizer, reduces the haze and the taste of a composite material, and reduces the discharge amount of VOC (volatile organic compound) gas.
The first aspect of the invention provides a plasticizer composite, and the preparation raw materials comprise diacid anhydride substances, alcohol substances, catalysts, alkaline water and filter aids.
The plasticizer preparation system of the invention is that acid substances and alcohol substances are subjected to esterification reaction under the action of a catalyst to form an ester mixture, and alkali water is utilized to neutralize unreacted acid substances in the reaction process, so that the residual acid substances are prevented from being doped in the plasticizer, and the performance of the plasticizer and the product is further influenced.
The alcohol substance is used as an important component of the plasticizer, the structure and the performance of the alcohol substance can greatly influence the performance of the obtained plasticizer and the plasticizer-containing product, the alcohol substance comprises n-decanol, and the applicant also has made a series of researches on the plasticizer containing the n-decanol, but the obtained plasticizer has a darker color, the chroma of the plasticizer is higher than No. 40 (measured by a platinum-cobalt method), the color depth of the composite material obtained by the plasticizer and PVC can be influenced, the application range of the obtained composite material is limited, and the problem is not solved for a long time.
Preferably, the carbonyl value of n-decanol is less than 40 mg/kg; further preferably, the carbonyl value of the decanol is less than 20 mg/kg; further preferably, the carbonyl value of decanol is less than 10 mg/kg; more preferably, the decanol is available from Fengyol industries, Inc.; in the experimental process, the applicant unexpectedly finds that when the raw material of the n-decanol with the carbonyl value of less than 20mg/kg is preferably adopted, the chroma of the obtained plasticizer can be obviously reduced to 25 (measured by a platinum-cobalt method), the yellowing resistance of the composite material of the plasticizer and PVC is also improved, because the carbonyl content of different n-decanol is different due to the component difference of the purchased raw materials, and when the carbonyl value of the n-decanol is controlled to be less than 20mg/kg, particularly the carbonyl value of the n-decanol purchased from Fengyol industries limited company is less than 5mg/kg, the carbonyl content of the plasticizer system is favorably lower, the oxidation degree is lower, the impurity content of the plasticizer and the structure variation of the impurity are less, so that the chroma of the plasticizer system GB/6324.6-1986 is reduced, and the yellowing resistance of the system is also improved.
The method for measuring the carbonyl value is GB/6324.6-1986.
The "carbonyl value of n-decanol" in the present invention means the carbonyl content in the raw material for purchase of n-decanol, which is produced during the production thereof and is present in the raw material for purchase.
The chromaticity of the plasticizer can be effectively reduced through the research of the scheme, but when the alcohol substance of the system is only n-decanol, the temperature resistance of the composite material of the plasticizer and PVC and the flexibility of the material are not ideal, and the temperature resistance of the composite material and the flexibility of the material are closely related to the effect of the plasticizer on PVC and also closely related to the structural composition of the plasticizer.
Further, the alcohol substance also comprises dodecanol and isodecanol, and preferably, the weight ratio of the dodecanol to the n-decanol to the isodecanol is controlled to be 1: (1.2-1.4): (0.8 to 1.2); more preferably 1: (1.25-1.35): (0.95-1.1); more preferably 1: 1.31: 1; the applicant also found unexpectedly in the course of experiments that when dodecanol, n-decanol and isodecanol are used together as the alcohol substance, especially when the weight ratio of dodecanol, n-decanol and isodecanol is 1: (1.2-1.4): (0.8-1.2), the haze, the chroma and the smell of the obtained plasticizer are improved, the temperature resistance and the flexibility of the composite material obtained by the obtained plasticizer and PVC are obviously improved, the haze, the chroma and the smell of the composite material obtained by the obtained plasticizer and PVC are also obviously superior to the haze, the chroma and the smell of the plasticizer only containing dodecanol and 2-propylheptanol (patent CN105237803), and the temperature resistance and the flexibility of the composite material formed by the plasticizer and a PVC matrix, which is probably because the dodecanol is a C12 straight chain, the n-decanol is a C10 straight chain, and the iso-decanol contains end side chains, the polarity of the formed plasticizer is in gradient distribution, the molecular volume is in gradient distribution, and the volume is in mutual cooperation, the volume concentration is increased, the volatilization of components is reduced, the haze and the smell are reduced, meanwhile, in the processing process of the PVC matrix material, the system compatibility is improved, the plasticizer can be better inserted among PVC molecules, the stress among the molecular chains is weakened, and the transferability of the PVC molecular chains is increased, meanwhile, plasticizers formed by the three alcohols are matched with each other, molecules interact with each other, migration of the plasticizers is reduced, and the temperature resistance and flexibility of the obtained PVC composite material are improved.
The diacid anhydride substance reacts with the alcohol substance to form an ester catalyst, and can be selected from any one or combination of more of glutaric anhydride, oxalic anhydride, succinic anhydride and phthalic anhydride; preferably phthalic anhydride; more preferably phthalic anhydride with the purity of more than or equal to 99.5 percent, the applicant finds that in the experimental process, when phthalic anhydride is adopted to act together with dodecanol, n-decanol and isodecanol, the problem of migration of the plasticizer can be effectively reduced, the aging resistance and the temperature resistance of the material are improved, the processability of compounding the plasticizer and the PVC matrix can be improved, the melt viscosity of the composite material in the processing process is reduced, and when terephthalic acid is adopted as an acid substance and is used as a plasticizer formed by alcohol substances, the polarity of the plasticizer is relatively low, the chroma of the formed plasticizer is increased, and when the phthalic anhydride is used, the migration rate is high, and the aging resistance and the temperature resistance of the PVC composite material are reduced; when trimellitic anhydride is used as a plasticizer formed by acids and alcohols, the chroma is increased, when the trimellitic anhydride is used, the plasticizer is poorer in processability when being compounded with a PVC matrix, the melt viscosity in the processing process is higher, for automobile interior manufacturers, the processing cost is increased, the probability of actual production and use is reduced, and probably, the migration rate is reduced because the approximation degree of the polarity of the plasticizer formed by the combined action of phthalic anhydride and the three alcohols and the polarity of a PVC system is higher than the approximation degree of the polarity of the plasticizer formed by terephthalic acid with a symmetrical structure and the polarity of the PVC system.
The invention does not specially limit the purchasing manufacturers of phthalic anhydride, such as but not limited to Shanghai Wallace New energy company; wherein, the purity of more than or equal to 99.5 percent means that the content of free acid in the raw material is less than the mass ratio of the purchased raw material and less than 0.5 percent.
In one embodiment, the weight ratio of the alcohol substance to the diacid anhydride substance is (2.5-3.5): 1; preferably, the weight ratio of the alcohol substance to the diacid anhydride substance is (2.9-3.1): 1; more preferably, the weight ratio of alcohol to diacid anhydride is 3: 1.
the catalyst of the present invention is used for the catalytic reaction of alcohol substances and diacid anhydride substances, and can be a catalyst well known to those skilled in the art, such as isopropyl titanate and the like; the content of the catalyst is 0.1-1 wt% of the alcohol substance; preferably 0.3 to 0.7wt per mill; more preferably 0.45 to 0.55 wt%.
The alkaline water is used for neutralizing unreacted acid substances in the reaction process of the acid substances and the alcohol substances, so that the residual acid substances are prevented from being doped in the plasticizer, the performance of the plasticizer and the performance of products are influenced, and well-known inorganic alkaline solutions such as a sodium hydroxide solution, a sodium carbonate solution, a potassium carbonate solution and a potassium hydroxide solution can be selected.
The dosage of the alkaline water is 1 to 5 weight per thousand of the content of the alcohol substances; preferably 2 to 4 weight per thousand; in one embodiment the alkaline water is a 10 wt% aqueous solution of sodium carbonate.
The filter aid is used for removing mechanical impurities in a system in the purification process of the obtained ester plasticizer, and the content of the filter aid is 0.3-1 per mill of the content of alcohols; preferably 0.5 to 0.7 per mill.
The filter aid is diatomite which has good microporous structure, adsorption performance and compression resistance, can not only ensure that the filtered liquid obtains better flow rate ratio, but also can filter fine suspended matters, and the applicant finds that the comprehensive performance of the obtained plasticizer is further improved when the diatomite with the model of SZ-308 is adopted for filter pressing in the experimental process.
The second aspect of the invention provides a preparation method of the plasticizer compound, which comprises four steps of esterification reaction, refining, pressure filtration and molecular distillation.
Preferably, the method for preparing the plasticizer composite comprises the following steps:
(1) esterification reaction: adding alcohols and diacid anhydrides into a reaction kettle, adding a catalyst, starting to pump air into the reaction kettle when the temperature is raised to 220 +/-10 ℃ to ensure that the kettle is in a negative pressure state, and continuing to start a vacuum pump to carry out negative pressure and dealcoholization when the esterification acid value is less than or equal to 0.1 mgKOH/g;
(2) refining: cooling the substances in the step (1), adding alkaline water for neutralization, heating and stripping while raising the temperature after neutralization, raising the temperature to 215 +/-10 ℃, keeping stripping for 2.5-4h, and ensuring that the central control index is qualified; preparing to enter a filter pressing operation;
(3) and (3) filter pressing: preserving the heat of the substances in the step (2) for 0.5h, then adding a filter aid for refining and stirring, and entering a molecular distillation stage after indexes are qualified after filter pressing;
(4) molecular distillation: performing molecular distillation on the substance obtained in the step (3), wherein the vacuum degree is less than or equal to 100pa, the inlet temperature of the material is kept at 190 +/-10 ℃, and the sample injection amount is 0.6-1.0 m3/h。
Further preferably, the preparation method of the plasticizer composite comprises the following steps:
(1) esterification reaction: firstly, adding the measured alcohol substances into a reaction kettle, opening a feed inlet after confirming that the temperature of the reaction kettle is lower than 80 ℃, adding the measured phthalic anhydride, covering the feed inlet, and starting stirring; charging nitrogen for 3-5 min, opening an oil valve to raise the temperature, opening a catalyst adding valve to add 0.2MPa N into a catalyst metering jar when the temperature of the kettle reaches 185 DEG C2Pressing the catalyst into an esterification kettle, adjusting a heat-conducting oil valve to control the temperature rising speed, and keeping the temperature rising speed at 15-20 ℃/h to prevent the material washing caused by excessively violent reaction after the catalyst is added; when the temperature rises to 220 +/-10 ℃, air is pumped into the reaction kettle to enable the kettle to be in a negative pressure state, so that water generated by esterification can be separated in time, and the reaction is accelerated to be carried out in the positive direction; when the esterification acid value is less than or equal to 0.1mgKOH/g, continuously starting a vacuum pump for negative pressure and dealcoholizing; when the alcohol bubbles in the kettle are less, the kettle is blackened;
(2) refining: cooling the substance in the step (1), adding alkaline water for neutralization, raising the temperature after neutralization and stripping simultaneously, and controlling the water amount at 100-400 kg/h; the temperature is increased to 215 +/-10 ℃, and the material temperature is kept to be 215 +/-10 ℃ in sequence and stably; ensuring the vacuum degree to be less than or equal to-0.095 Mpa, keeping steam stripping for 2.5-4h, and sampling to measure flash point and acid value when less stripping substances are observed in the effluent; the flash point of the central control semi-finished product is more than or equal to 230 ℃, the acid value is less than or equal to 0.05mgKOH/g, and a heat transfer oil valve is closed to prepare for entering the filter pressing operation;
(3) and (3) filter pressing: firstly, using steam-lift water to cool the material obtained in the step (2) to 120 +/-10 ℃, and keeping the temperature for 30min, wherein nitrogen is filled for 3-5 times in the heat preservation process; then adding a filter aid for refining and stirring, and entering a molecular distillation stage after indexes are qualified after filter pressing;
(4) molecular distillation: performing molecular distillation on the substance obtained in the step (3), wherein the vacuum degree is less than or equal to 100pa, the inlet temperature of the material is kept at 190 +/-10 ℃, and the sample injection amount is 0.6-1.0 m3H; keeping the sample introduction frequency at 20 +/-5 HZ, and automatically separating and purifying the light and heavy components of the product in molecular distillation equipment; collecting heavy component finished products, and transferring the heavy component finished products to a finished product tank for storage after the heavy component finished products are detected to be qualified; the scraper blade in the molecular distillation equipment scrapes the heated material into a film shape, so that the evaporation area of the material is effectively increased, low-boiling-point substances in the material are quickly evaporated, the purity of the product is improved, the atomization degree is improved, the volatility is reduced, and the odor is reduced.
The third aspect of the invention provides a PVC composite material for vehicle decoration, which comprises a PVC base material and the plasticizer compound; preferably, a stabilizer is also included.
Preferably, the PVC composite material for the automobile decoration comprises, by weight, 95-115 parts of a PVC base material, 30-50 parts of the plasticizer compound and 2-5 parts of a stabilizer; further preferably, the PVC composite material comprises 100-105 parts of PVC base material, 40-45 parts of the plasticizer composite and 3-4 parts of stabilizer.
The stabilizers are well known to those skilled in the art, such as, but not limited to: 318 stabilizer such as zinc stearate, barium stearate, etc.; the PVC base material is PVC pellets which are customary to the person skilled in the art.
The PVC composite material for automobile decoration may be prepared by a preparation method well known to those skilled in the art, and the preparation method of the PVC composite material for automobile decoration is not particularly limited in the present invention.
Example 1
The embodiment 1 of the invention provides a plasticizer, which is prepared from the following raw materials of diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.4: 1.2; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3.5: 1;
the content of the catalyst is 0.7wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 4wt per mill of the content of the alcohol; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308; the content of the filter aid is 1 per mill of the content of the alcohol substances;
the preparation method of the plasticizer compound comprises the following steps:
(1) esterification reaction: firstly adding the measured alcohol substances into a reaction kettle, opening a feed inlet after the temperature of the reaction kettle is confirmed to be lower than 80 ℃, adding the measured phthalic anhydride, covering the feed inlet, and starting stirring; charging nitrogen for 3-5 min, opening an oil valve to raise the temperature, opening a catalyst adding valve to add 0.2MPa N into a catalyst metering jar when the temperature of the kettle reaches 185 DEG C2Pressing the catalyst into an esterification kettle, adjusting a heat-conducting oil valve to control the temperature rising speed, and keeping the temperature rising speed at 15-20 ℃/h to prevent the material washing caused by excessively violent reaction after the catalyst is added; when the temperature rises to 220 +/-10 ℃, air is pumped into the reaction kettle to enable the kettle to be in a negative pressure state, so that water generated by esterification can be separated in time, and the reaction is accelerated to be carried out in the positive direction; when the esterification acid value is less than or equal to 0.1mgKOH/g, continuously starting a vacuum pump for negative pressure and dealcoholization; when the alcohol bubbles in the kettle are less, the kettle is blackened;
(2) refining: cooling the substance in the step (1), adding alkaline water for neutralization, raising the temperature after neutralization and stripping simultaneously, and controlling the water amount at 100-400 kg/h; the temperature is increased to 215 +/-10 ℃, and the material temperature is kept to be in a step of stabilizing at 215 +/-10 ℃; ensuring the vacuum degree to be less than or equal to-0.095 Mpa, keeping steam stripping for 2.5-4h, and sampling to measure flash point and acid value when few substances are removed from the effluent; the flash point of the intermediate control semi-finished product is more than or equal to 230 ℃, the acid value is less than or equal to 0.05mgKOH/g, and a heat-conducting oil valve is closed for entering the filter pressing operation;
(3) and (3) filter pressing: firstly, using steam-lift water to cool the material obtained in the step (2) to 120 +/-10 ℃, and keeping the temperature for 30min, wherein nitrogen is filled for 3-5 times in the heat preservation process; then adding a filter aid for refining and stirring, and entering a molecular distillation stage after indexes are qualified after filter pressing;
(4) molecular distillation: performing molecular distillation on the substance obtained in the step (3), wherein the vacuum degree is less than or equal to 100pa, the inlet temperature of the material is kept at 190 +/-10 ℃, and the sample injection amount is 0.8m3H; keeping the sample introduction frequency at 20 +/-5 HZ, and automatically separating and purifying the light and heavy components of the product in molecular distillation equipment; and collecting the heavy component finished product, and transferring the heavy component finished product to a finished product tank for storage after the heavy component finished product is detected to be qualified.
Example 2
The embodiment 2 of the invention provides a plasticizer, which is prepared from the following raw materials of diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.2: 0.8; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 2.5: 1;
the content of the catalyst is 0.3wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 2wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite which is SZ-308; the content of the filter aid is 0.3 per mill of the content of the alcohol substances;
the plasticizer composite was prepared in the same manner as in example 1.
Example 3
Embodiment 3 of the present invention provides a plasticizer, which is prepared from the following raw materials of diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.31: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite which is SZ-308; the content of the filter aid is 0.62 per mill of the content of the alcohol substances;
the plasticizer composite was prepared in the same manner as in example 1.
Example 4
Embodiment 4 of the present invention provides a plasticizer, which is prepared from the following raw materials, namely, diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol and isodecanol, and the weight ratio of the dodecanol to the isodecanol is 1: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 5
Embodiment 5 of the present invention provides a plasticizer, which is prepared from the following raw materials, namely, a diacid anhydride substance, an alcohol substance, a catalyst, alkaline water and a filter aid;
the alcohols are n-decanol and iso-decanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the n-decanol to the iso-decanol is 1.31: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite which is SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 6
Embodiment 6 of the present invention provides a plasticizer, which is prepared from the following raw materials, namely, a diacid anhydride substance, an alcohol substance, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Liaoning Huaxing group chemical company, and the carbonyl value is 80 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.31: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 7
Example 7 of the present invention provides a plasticizer prepared from a starting material comprising a diacid anhydride compound, an alcohol compound, a catalyst, an alkali water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.31: 1; replacing diacid anhydride substances with trimellitic anhydride; the weight ratio of the alcohol substance to the trimellitic anhydride is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 8
Embodiment 8 of the present invention provides a plasticizer, which is prepared from the following raw materials, namely, a diacid anhydride substance, an alcohol substance, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.31: 1; replacing the diacid anhydride type substance by terephthalic acid; the weight ratio of the alcohol substance to the terephthalic acid is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 9
Example 9 of the present invention provides a plasticizer prepared from a starting material comprising a diacid anhydride compound, an alcohol compound, a catalyst, an alkali water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 0.85: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5 wt% of the alcohol; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 10
The embodiment 10 of the invention provides a plasticizer, which is prepared from the following raw materials of diacid anhydride substances, alcohol substances, a catalyst, alkaline water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 2: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-308;
the plasticizer composite was prepared in the same manner as in example 1.
Example 11
Example 11 of the present invention provides a plasticizer prepared from a starting material comprising a diacid anhydride compound, an alcohol compound, a catalyst, an alkali water and a filter aid;
the alcohols are dodecanol, n-decanol and isodecanol, the n-decanol is purchased from Fengyi alcohol industry Co., Ltd, and the carbonyl value is 1.9 mg/kg; the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: 1.31: 1; the diacid anhydride substance is phthalic anhydride with the purity of more than or equal to 99.5 percent; the weight ratio of the alcohol substance to the diacid anhydride substance is 3: 1;
the content of the catalyst is 0.5wt per mill of the alcohol substance; the catalyst is isopropyl titanate;
the dosage of the alkaline water is 3.6wt per mill of the content of the alcohol substances; the alkaline water is 10 wt% sodium carbonate aqueous solution;
the filter aid is diatomite and SZ-309;
the plasticizer composite was prepared in the same manner as in example 1.
Control group 1
The control group of the invention is DOP which is universal in China.
Control group 2
The control group of the invention is DPHP which is universal in China.
Control group 3
The control group of the present invention was 911P commonly used in China.
Control group 4
The control group of the present invention is a domestic general V124.
Performance evaluation
1. The physical and chemical properties of the plasticizer obtained in example 3 were measured, and the details and results are shown in table 1 below:
TABLE 1
| Inspection item | Test results | Inspection method |
| Appearance of the product | Transparent and impurity-free | Visual inspection of |
| Color number (platinum-cobalt) | 20 | GB/T 1664 |
| Acid value of mgKOH/g | 0.019 | GB/T 1668 |
| Specific gravity, (20/20 deg.C) | 0.960 | GB/T 4472 |
| The ester content wt% | 99.8 | GC |
| Water content wt% | 0.029 | GB/T 6283 |
| Flash point (open cup method) deg.C | 235 | GB/T 1671 |
| Free alcohol content Ppm w/w | 50 | GC |
2. The degree of atomization of the plasticizer in example 3 and the control groups 1 to 4 was measured by DIN75201/B method, and the plasticizing rate of the plasticizer in example 3 and the control groups 1 to 4 was calculated, the results are shown in table 2 below:
TABLE 2
Wherein, the substitution coefficient is the ratio of the plasticizer Part (PHR) reaching the requirement of Shore hardness (A)80 to the DOP dosage (52.9 parts) at room temperature.
3. Environmental protection test
TABLE 3
Undetected (less than method detection limit)
TABLE 4
Example 3 of the present invention can also be tested by REACH regulation.
4. The same test method as that of example 3 was used to test the chromaticity and haze of examples 1 to 2 and 4 to 11;
5. odor: judging the odor of the obtained plasticizer in the actual use process by olfaction, wherein the evaluation results are divided into no taste, small odor and large odor;
TABLE 5
| Color intensity | Haze degree | Smell(s) | |
| Example 1 | 22 | 0.12 | Is tasteless |
| Example 2 | 22 | 0.12 | Is tasteless |
| Example 3 | 20 | 0.1 | Is tasteless |
| Example 4 | 30 | 0.3 | Big smell |
| Example 5 | 25 | 0.35 | Has little smell |
| Example 6 | 55 | 0.2 | Has little smell |
| Example 7 | 35 | 0.12 | Has little smell |
| Example 8 | 30 | 0.12 | Has little smell |
| Example 9 | 25 | 0.2 | Has little smell |
| Example 10 | \ | 0.12 | Is tasteless |
| Example 11 | 30 | \ | \ |
6. Preparing a PVC composite material by using the plasticizers obtained in the embodiments 1 to 9 and 11, wherein the PVC composite material comprises 102 parts by weight of a PVC base material, 43 parts by weight of the plasticizer composite and 3 parts by weight of a stabilizer, and the stabilizer is zinc stearate; the preparation process of the PVC composite material comprises the following steps: uniformly mixing and stirring a PVC base material, a plasticizer and a stabilizer by a mixer to form a mixture; conveying the mixture to a calender through a filter for high-temperature melting calendering at the temperature of 150-160 ℃ to obtain a calendered primary automotive interior material; the PVC base material is PVC granules which are purchased from the industry of huge sources;
a-measuring the temperature resistance and low temperature resistance of the obtained PVC composite material: placing the obtained PVC composite material at-20 ℃ for 48h, and observing whether the PVC composite material is broken or not; each example corresponds to 50 samples, and the evaluation results are divided into: a-the number of fractures is 0-3; b-the number of the fractures is 4-10; the number of C-fractures is 11-20; d-number of breaks is more than or equal to 20; high temperature resistance: the obtained PVC composite material is placed at 60 ℃ for 48 hours, the taste degree of the material is observed, and the evaluation results are divided into no taste, small smell and big smell;
b-measuring the yellowing resistance of the obtained PVC composite material, placing the obtained PVC composite material at 60 ℃ for 7 days, observing whether the obtained PVC composite material is yellowed or not, wherein each embodiment corresponds to 50 samples, and the evaluation results are as follows: a-the number of yellowing is 0-3; b-the number of yellowing is 4-10; the number of C-yellowing is 11-20; the number of D-yellowing is more than or equal to 20;
c-observing the quality of the processing performance in the preparation process of the PVC composite material, and evaluating the result: the viscosity of the system is high in the processing process, the fluidity is poor, and the processability is poor; the viscosity is proper in the processing process, the fluidity is good, and the processing performance is good.
TABLE 6
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as can be conceived and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (4)
1. The plasticizer compound is characterized in that the preparation raw materials comprise diacid anhydride substances, alcohol substances, catalysts, alkaline water and filter aids; wherein the alcohol comprises n-decanol;
the alcohols also comprise dodecanol and isodecanol;
the weight ratio of the dodecanol to the n-decanol to the iso-decanol is 1: (1.25-1.35): (0.95-1.1);
the diacid anhydride substance is phthalic anhydride;
the weight ratio of the alcohol substance to the diacid anhydride substance is (2.5-3.5): 1;
the purity of the diacid anhydride substances is more than or equal to 99.5 percent;
the carbonyl value of the n-decanol is less than 10 mg/kg.
2. A method for preparing a plasticizer composite according to claim 1, comprising four steps of esterification, refining, pressure filtration, and molecular distillation.
3. The method of preparing a plasticizer composite according to claim 2, comprising the steps of:
(1) esterification reaction: adding alcohols and diacid anhydrides into a reaction kettle, adding a catalyst, starting to pump air into the reaction kettle when the temperature is raised to 220 +/-10 ℃ to ensure that the kettle is in a negative pressure state, and continuing to start a vacuum pump to carry out negative pressure and dealcoholization when the esterification acid value is less than or equal to 0.1 mgKOH/g;
(2) refining: cooling the substances in the step (1), adding alkaline water for neutralization, heating and stripping while raising the temperature after neutralization, raising the temperature to 215 +/-10 ℃, keeping stripping for 2.5-4h, and ensuring that the central control index is qualified; preparing to enter a filter pressing operation;
(3) and (3) filter pressing: preserving the heat of the substances in the step (2) for 0.5h, then adding a filter aid for refining and stirring, and entering a molecular distillation stage after indexes are qualified after filter pressing;
(4) molecular distillation: performing molecular distillation on the substance obtained in the step (3), wherein the vacuum degree is less than or equal to 100pa, the inlet temperature of the material is kept at 190 +/-10 ℃, and the sample injection amount is 0.6-1.0 m3/h。
4. A PVC composite for automotive trim comprising a PVC base material and the plasticizer composite of claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237401A (en) * | 2015-10-16 | 2016-01-13 | 江苏森禾化工科技有限公司 | Manufacturing technology of plasticizer |
| CN105254495A (en) * | 2014-07-09 | 2016-01-20 | 江苏森禾化工科技有限公司 | Production method of functional environmental-protection plasticizer with characteristics of high-temperature-resistance, low-temperature-resistance and low fogging degree |
| CN106497071A (en) * | 2016-11-28 | 2017-03-15 | 江苏森禾化工科技有限公司 | A kind of high strength linear composite elasticizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105254495A (en) * | 2014-07-09 | 2016-01-20 | 江苏森禾化工科技有限公司 | Production method of functional environmental-protection plasticizer with characteristics of high-temperature-resistance, low-temperature-resistance and low fogging degree |
| CN105237401A (en) * | 2015-10-16 | 2016-01-13 | 江苏森禾化工科技有限公司 | Manufacturing technology of plasticizer |
| CN106497071A (en) * | 2016-11-28 | 2017-03-15 | 江苏森禾化工科技有限公司 | A kind of high strength linear composite elasticizer |
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