CN113444343B - Preparation method of hyperbranched microcrystalline nucleating agent and preparation method of polyolefin resin - Google Patents
Preparation method of hyperbranched microcrystalline nucleating agent and preparation method of polyolefin resin Download PDFInfo
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Abstract
The invention discloses a preparation method of a hyperbranched microcrystalline nucleating agent and a preparation method of polyolefin resin. The hyperbranched microcrystalline nucleating agent is prepared by mixing an organic metal salt nucleating agent, hyperbranched aromatic polyester and fatty acid amide selected from the group consisting of optionally added fatty acid amide, and performing spray drying. Through the interaction between the three-dimensional structure of the hyperbranched aromatic polyester and a large number of active groups on the surface and the organic metal salt nucleating agent, symbiotic microcrystals are formed in the spray drying process, and the dispersion degree of the organic metal salt nucleating agent in matrix resin is improved, so that the mechanical and heat resistance of plastic products can be improved, and the hyperbranched aromatic polyester can be applied to the preparation of polyolefin resin.
Description
Technical Field
The invention relates to the field of polymer modification processing, in particular to a preparation method of a hyperbranched microcrystalline nucleating agent and a preparation method of polyolefin resin.
Background
Regulating the crystallization of semi-crystalline resins is an important means of improving their performance and increasing functionality. A nucleating agent is a modifier that promotes crystallization of a polymer and improves its grain structure. The addition of the nucleating agent to the semi-crystalline resin accelerates the crystallization rate of the semi-crystalline resin, increases the mechanical properties and processability of the semi-crystalline resin, and improves the thermodynamic properties of the semi-crystalline resin. Depending on the state of the nucleating agent at the melting temperature of the semi-crystalline resin, existing commercial nucleating agents can be divided into: particle dispersion type nucleating agents and meltable nucleating agents at processing temperatures. The particle dispersion type nucleating agent has higher melting point, can not be melted in the processing process of semi-crystalline resin, can only be dispersed in matrix resin, and can be used as a nucleation point to induce heterogeneous nucleation of the matrix resin so as to promote crystallization. Therefore, in a certain range, the higher the concentration of the particle-type nucleating agent, the better the nucleating effect. The smaller the particles of the particle dispersion type nucleating agent, the more nucleation points, the smaller the size of the induced spherulites, the more excellent the mechanical properties of the final product and the higher the temperature resistance degree.
Most of the existing organic metal salt nucleating agents have high melting point, poor dispersibility and low nucleating effect. The prior technical science is solved by the following means: (1) dissolving and dispersing the mixture in an alcohol solvent, and then recrystallizing; (2) compounding a plurality of metal organic salt nucleating agents; (3) Aliphatic monobasic acid or aliphatic monobasic acid metal salt compounding, etc. Although the dispersion degree of the organic metal salt nucleating agent is improved to a certain degree, certain defects still exist due to the problems of smell, environmental protection and the like.
Therefore, controlling the crystal growth of the organometallic salt nucleating agent is a difficulty in improving the dispersibility of the nucleating agent in the matrix resin.
Disclosure of Invention
The object of the present invention is at least to solve the above mentioned technical problems. The inventor creatively thinks that the three-dimensional space structure of the hyperbranched polymer and the interaction between a large number of active groups on the surface and the organic metal salt nucleating agent are utilized in the research process, so that the hyperbranched polymer and the organic metal salt nucleating agent form symbiotic microcrystals in the spray drying process, and the dispersion degree of the organic metal salt nucleating agent in matrix resin is improved. Therefore, the mechanical property, the thermal deformation temperature, the transparency and the like of the resin are effectively improved, and an effective solution is provided for the nucleating agent with low cost and excellent performance.
Specifically, the invention provides the following technical scheme:
in a first aspect of the invention, the invention provides a method for preparing a hyperbranched microcrystalline nucleating agent, comprising: the organic metal salt nucleating agent, hyperbranched aromatic polyester and optionally added fatty acid amide are mixed and spray-dried to obtain the organic metal salt nucleating agent.
First, by the interaction between the organometallic salt and the hyperbranched aromatic polyester, the organometallic salt is accelerated to melt faster during the resin processing temperature rise. Secondly, in the resin processing and cooling process, hydrogen bonds and pi-pi interactions between the organic metal salt and the hyperbranched aromatic polyester form hyperbranched microcrystals, so that the organic metal salt can be dispersed on the three-dimensional surface of the hyperbranched polymer, the mutual aggregation among organic metal salt molecules is weakened, the dispersion of the organic metal salt in matrix resin is improved, the nucleation point of the matrix resin is increased in multiple, the crystallization process of the matrix resin is accelerated, and the crystallinity is improved. In addition, the surface of the hyperbranched microcrystal can be modified through hydrogen bond action by additionally adding fatty acid amide, and the compatibility between the hyperbranched microcrystal and the matrix resin is regulated, so that the nucleation effect of the hyperbranched microcrystal nucleating agent is further improved.
Further, the preparation method of the hyperbranched microcrystalline nucleating agent provided above may further include the following technical features:
further, the organometallic-based nucleating agent is selected from the group consisting of: at least one of a metal monocyclocarboxylate, a metal bicyclocarboxylate and a metal substituted heteroaromatic phosphate. The monocyclic carboxylic acid metal salts include, but are not limited to: at least one of sodium benzoate, calcium benzoate, sodium phthalate, sodium p-tert-butylbenzoate, aluminum p-tert-butylbenzoate and hexahydrophthalic acid metal salt. The metal salts of bicyclic carboxylic acids include, but are not limited to: at least one of disodium bicycloheptane dicarboxylate, calcium bicycloheptane dicarboxylate and disodium bicyclooctane dicarboxylate. The aromatic metal phosphate includes, but is not limited to, at least one of sodium p-tert-butylphenyl phosphate, sodium bis (p-tert-butylphenyl) phosphate (NA-10), sodium 2,2 methylenebis (4, 6-di-tert-butylphenyl) phosphate (NA-11), and basic aluminum 2,2 methylenebis (4, 6-di-tert-butylphenyl) phosphate (NA-21).
Further, the average grain diameter of the hyperbranched microcrystalline nucleating agent is smaller than 100 microns. The particle size of the nucleating agent can affect the final nucleation effect. The inventors found during the course of the study that above the above-mentioned dimensions, the nucleation effect drastically decreased; below the above-mentioned size, the increase in nucleation effect is not significant, but the decrease in processing cost due to the decrease in particle size increases sharply.
Further, the weight average molecular weight of the hyperbranched aromatic polyester is 500-6000; the weight average molecular weight of the hyperbranched aromatic polyester has a great influence on the nucleation effect. The weight average molecular weight of the hyperbranched aromatic polyester is improved to be beneficial to improving the nucleation effect of the hyperbranched microcrystalline nucleating agent. When the molecular weight exceeds the optimal molecular weight, the weight average molecular weight of the hyperbranched aromatic polyester is increased, so that the nucleation effect of the final hyperbranched microcrystalline nucleating agent is weakened due to poor dispersibility of the hyperbranched aromatic polyester. Preferably, the weight average molecular weight of the hyperbranched aromatic polyester is 1000-3000.
Further, the hyperbranched aromatic polyester is carboxyl-terminated hyperbranched aromatic polyester with carboxylic acid as a terminal group. Preferably, the hyperbranched aromatic polyester is benzoic acid-terminated hyperbranched aromatic polyester, phthalic acid-terminated hyperbranched aromatic polyester or terephthalic acid-terminated hyperbranched aromatic polyester.
Further, the hyperbranched aromatic polyester is obtained by the following method:
(1) Adding polybasic aromatic carboxylic acid/anhydride and polyhydric alcohol into a reactor, adding a catalyst, and reacting for 1-4 hours at 40-120 ℃ under the protection of inert gas;
(2) Adding bisoxazoline, raising the temperature to 100-250 ℃, vacuumizing the reaction system, and continuously reacting for 1-24 hours under the condition of reduced pressure to prepare the hyperbranched aromatic polyester.
Further, the polybasic aromatic carboxylic acid/anhydride is a carboxylic acid aromatic organic matter with carboxyl group functionality not less than 2. For example, the polyaromatic carboxylic acids/anhydrides include, but are not limited to, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride.
The polyol is an alcohol organic matter with hydroxyl functionality not less than 2. For example, the polyols include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, xylitol, sorbitol, and the like.
Further, the catalyst is an ester condensation catalyst selected from the group consisting of: at least one of sulfuric acid, toluene sulfonic acid, butyl titanate, dibutyl tin dilaurate, stannous chloride and stannous octoate.
The bisoxazoline is selected from the group consisting of: at least one of 1, 3-bisoxazoline, 2- (1, 3-phenylene) bis (2-oxazoline), 2-bis (2-oxazoline), 1, 4-bis (2-oxazolinyl) benzene.
Further, the molar ratio of the polybasic aromatic carboxylic acid/anhydride to the polyhydric alcohol is 1:0.5 to 2; the catalyst is 0-10% of the mole number of the polybasic aromatic carboxylic acid/anhydride; the bisoxazoline accounts for 0 to 20 percent of the mole number of the polybasic aromatic carboxylic acid/anhydride.
Further, it contains 50 to 90 parts by weight of an organometallic nucleating agent, 1 to 50 parts by weight of a hyperbranched aromatic polyester, and 0 to 20 parts by weight of a fatty acid amide. The organometallic salt acts as the primary nucleation site; the hyperbranched aromatic polyester is used as a nucleation aiding agent of organic metal salt, the higher the proportion is, the more the nucleation effect can be improved, and the final nucleation effect is not improved any more by the hyperbranched polymer exceeding the optimal proportion. Further, the composition contains 60 to 80 weight parts of organic metal nucleating agent, 1 to 30 weight parts of hyperbranched aromatic polyester of A-class compound and 0 to 20 weight parts of fatty acid amide.
Further, the preparation method of the hyperbranched microcrystalline nucleating agent comprises the following steps: (1) Dissolving an organic metal salt nucleating agent, hyperbranched aromatic polyester and optionally added fatty acid amide to form a raw material solution; (2) Carrying out ultrasonic treatment on the raw material solution so as to obtain a uniformly dispersed solution; (3) And (3) spray drying the solution obtained in the step (2) in a spray mode to obtain a spray-dried product, and thus the hyperbranched microcrystalline nucleating agent is obtained. The solvent used in the dissolution process is not particularly limited and may be, for example, at least one of the following: acetone, methylene chloride, methanol, ethanol, propanol, isopropanol, butanol, petroleum ether, tetrahydrofuran, ethyl acetate, toluene and 1, 4-dioxane.
Further, the time of the ultrasonic treatment is 5 to 30 minutes, whereby a uniformly dispersed solution can be obtained.
Further, the air inlet temperature of the spray drying is 110-200 ℃, and the air outlet temperature of the spray drying is 0-90 ℃.
In a second aspect of the present invention, there is provided a method for producing a polyolefin resin, comprising: the hyperbranched microcrystalline nucleating agent is obtained by mixing and melting the hyperbranched microcrystalline nucleating agent and the polyolefin matrix resin, and the hyperbranched microcrystalline nucleating agent is prepared and obtained according to the method of any embodiment of the first aspect of the invention.
The beneficial effects obtained by the invention are as follows:
(1) The preparation method of the hyperbranched microcrystalline nucleating agent provided by the invention has the advantages that in the processing temperature rising process, the hyperbranched aromatic polyester promotes the melting of the organic metal salt, and the dispersion of the organic metal salt in matrix resin is improved.
(2) According to the preparation method of the hyperbranched microcrystalline nucleating agent, in the processing and cooling process, hyperbranched aromatic polyester can form eutectic in cooperation with the organic metal salt to form hyperbranched microcrystalline nucleating agent, aggregation of the organic metal salt is reduced, dispersion of the microcrystalline in matrix resin is improved, and therefore the nucleating effect of the hyperbranched microcrystalline nucleating agent is improved.
(3) According to the preparation method of the hyperbranched microcrystalline nucleating agent, provided by the invention, the fatty amide is added to regulate and control the compatibility of the hyperbranched microcrystalline nucleating agent and the matrix resin, so that the nucleation effect of the hyperbranched microcrystalline nucleating agent is further improved.
Detailed Description
The following detailed description of embodiments of the invention, it should be noted that the described embodiments are exemplary and intended to be illustrative of the invention and should not be construed as limiting the invention.
In a first aspect of the invention, the invention provides a method for preparing a hyperbranched microcrystalline nucleating agent, comprising: the organic metal salt nucleating agent, hyperbranched aromatic polyester and fatty acid amide are mixed and spray-dried to obtain the organic metal salt nucleating agent. First, by the interaction between the organometallic salt and the hyperbranched aromatic polyester, the organometallic salt is accelerated to melt faster during the resin processing temperature rise. Secondly, in the resin processing and cooling process, hydrogen bonds and pi-pi interactions between the organic metal salt and the hyperbranched polymer form hyperbranched microcrystals, so that the organic metal salt can be dispersed on the three-dimensional surface of the hyperbranched polymer, the mutual aggregation among organic metal salt molecules is weakened, the dispersion of the organic metal salt in matrix resin is improved, the nucleation point of the matrix resin is increased in multiple, the crystallization process of the matrix resin is accelerated, and the crystallinity is improved. In addition, the surface of the hyperbranched microcrystal can be modified through hydrogen bond action by additionally adding fatty acid amide, and the compatibility between the hyperbranched microcrystal and the matrix resin is regulated, so that the nucleation effect of the hyperbranched microcrystal nucleating agent is further improved.
The organometallic-based nucleating agent includes, but is not limited to: at least one of a metal monocyclocarboxylate, a metal bicyclocarboxylate and a metal substituted heteroaromatic phosphate. The monocyclic carboxylic acid metal salts include, but are not limited to: at least one of sodium benzoate, calcium benzoate, sodium phthalate, sodium p-tert-butylbenzoate, aluminum p-tert-butylbenzoate and hexahydrophthalic acid metal salt. The metal salts of bicyclic carboxylic acids include, but are not limited to: at least one of disodium bicycloheptane dicarboxylate, calcium bicycloheptane dicarboxylate and disodium bicyclooctane dicarboxylate. The aromatic metal phosphate includes, but is not limited to, at least one of sodium p-tert-butylphenyl phosphate, sodium bis (p-tert-butylphenyl) phosphate (NA-10), sodium 2,2 methylenebis (4, 6-di-tert-butylphenyl) phosphate (NA-11), and basic aluminum 2,2 methylenebis (4, 6-di-tert-butylphenyl) phosphate (NA-21).
The average grain diameter of the hyperbranched microcrystalline nucleating agent is smaller than 100 microns. The particle size of the nucleating agent can affect the final nucleation effect. The inventors found during the course of the study that above the above-mentioned dimensions, the nucleation effect drastically decreased; below the above-mentioned size, the increase in nucleation effect is not significant, but the decrease in processing cost due to the decrease in particle size increases sharply. In at least some embodiments, the hyperbranched microcrystalline nucleating agent has an average particle size of less than 100 microns, such as less than 90 microns, less than 80 microns, less than 70 microns, less than 60 microns, less than 50 microns, less than 40 microns, less than 20 microns, less than 10 microns.
The weight average molecular weight of the hyperbranched aromatic polyester is 500-6000, and can be 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500 or 5000, 5500, 6000, etc. The weight average molecular weight of the hyperbranched aromatic polyester has a great influence on the nucleation effect. The weight average molecular weight of the hyperbranched aromatic polyester is improved to be beneficial to improving the nucleation effect of the hyperbranched microcrystalline nucleating agent. When the molecular weight exceeds the optimal molecular weight, the weight average molecular weight of the hyperbranched aromatic polyester is increased, so that the nucleation effect of the final hyperbranched microcrystalline nucleating agent is weakened due to poor dispersibility of the hyperbranched aromatic polyester. In at least some embodiments, the hyperbranched aromatic polyesters have a weight-average molecular weight ranging from 1000 to 5000, alternatively from 1000 to 3000. In at least some preferred embodiments, the hyperbranched aromatic polyesters have a weight-average molecular weight ranging from 2000 to 3000.
The hyperbranched aromatic polyester is carboxyl-terminated hyperbranched aromatic polyester with carboxylic acid as a terminal group. In at least some embodiments, the hyperbranched aromatic polyester is a benzoic-terminated hyperbranched aromatic polyester, a phthalic-terminated hyperbranched aromatic polyester, a terephthalic-terminated hyperbranched aromatic polyester.
In at least some embodiments, the hyperbranched aromatic polyester is obtained by a process comprising:
(1) Adding polybasic aromatic carboxylic acid/anhydride and polyhydric alcohol into a reactor, adding a catalyst, and reacting for 1-4 hours at 40-120 ℃ under the protection of inert gas;
(2) Adding bisoxazoline, raising the temperature to 100-250 ℃, vacuumizing the reaction system, and continuously reacting for 1-24 hours under the condition of reduced pressure to prepare the hyperbranched aromatic polyester.
In at least some embodiments, the polyaromatic carboxylic acid/anhydride comprises: trimesic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, and the like; the polyol is selected from the group consisting of: ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, xylitol, sorbitol, and the like.
The catalyst is an ester condensation catalyst selected from the group consisting of: at least one of sulfuric acid, toluene sulfonic acid, butyl titanate, dibutyl tin dilaurate, stannous chloride and stannous octoate;
the bisoxazoline is selected from the group consisting of: at least one of 1, 3-bisoxazoline, 2- (1, 3-phenylene) bis (2-oxazoline), 2-bis (2-oxazoline), 1, 4-bis (2-oxazolinyl) benzene.
In at least some embodiments, the molar ratio of the polyaromatic carboxylic acid/anhydride to the polyol is 1:0.5 to 2; the catalyst is 0-10% of the mole number of the polybasic aromatic carboxylic acid/anhydride; the bisoxazoline accounts for 0 to 20 percent of the mole number of the polybasic aromatic carboxylic acid/anhydride.
In at least some embodiments, the hyperbranched microcrystalline nucleating agent comprises 50 to 90 parts by weight of an organometallic-based nucleating agent, 1 to 50 parts by weight of a hyperbranched aromatic polyester, and 0 to 20 parts by weight of a fatty acid amide. The organic metal salt is used as a main nucleation point, the hyperbranched polymer is used as a nucleation aiding agent of the organic metal salt, the higher the proportion is, the more the nucleation effect can be improved, and the final nucleation effect is not improved any more by the hyperbranched polymer in excess of the optimal proportion. In some preferred embodiments, the composition contains 60 to 80 parts by weight of an organometallic-based nucleating agent, 1 to 30 parts by weight of a hyperbranched aromatic polyester, and 0 to 20 parts by weight of a fatty acid amide. In some preferred embodiments, the composition contains 60 to 80 parts by weight of an organometallic-based nucleating agent, 1 to 30 parts by weight of a hyperbranched aromatic polyester, and 5 to 20 parts by weight of a fatty acid amide.
Further, the preparation method of the hyperbranched microcrystalline nucleating agent comprises the following steps: (1) Dissolving an organic metal salt nucleating agent, hyperbranched aromatic polyester and optionally added fatty acid amide to form a raw material solution; (2) ultrasonic treatment for 5-30 min; (3) And (3) spray-drying the solution which is obtained in the step (2) and is uniformly dispersed in a spray mode to obtain a spray-dried product, and thus the hyperbranched microcrystalline nucleating agent is obtained. The solvent used in the dissolution process is at least one of the following: acetone, methylene chloride, methanol, ethanol, propanol, isopropanol, butanol, petroleum ether, tetrahydrofuran, ethyl acetate, toluene and 1, 4-dioxane. The air inlet temperature of the spray drying is 110-200 ℃, and the air outlet temperature of the spray drying is 0-90 ℃.
In a second aspect of the present invention, there is provided a method for producing a polyolefin resin, comprising: the hyperbranched microcrystalline nucleating agent is obtained by mixing and melting the hyperbranched microcrystalline nucleating agent and the polyolefin matrix resin, and the hyperbranched microcrystalline nucleating agent is prepared and obtained according to the method of any embodiment of the first aspect of the invention.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In addition, for convenience of description, the organometallic nucleating agent used in the following examples is also referred to as a class a substance, the hyperbranched aromatic polyester is also referred to as a class B substance, and the fatty acid amide is also referred to as a class C substance.
Example 1
Example 1 hyperbranched microcrystalline nucleants were prepared using different class B materials. In addition, example 1 also investigated the effect of spray drying on the hyperbranched microcrystalline nucleants of the invention.
Experimental group 1-1
The hyperbranched aromatic polyester is first prepared as follows:
the molar ratio of the trimesic acid to the glycol is 1:0.5 is added into a reactor, and then toluene sulfonic acid (the molar quantity of which is 10 percent of that of trimesic acid) serving as a catalyst is added, and the mixture is reacted for 1 hour at 80 ℃ under the protection of inert gas nitrogen; then adding 1, 3-bisoxazoline (the molar quantity of which is 20 percent of that of trimesic acid), raising the temperature to 120 ℃, vacuumizing the reaction system, and continuously reacting for 1 hour under the condition of reduced pressure to prepare the hyperbranched aromatic polyester. The hyperbranched aromatic polyester has a weight-average molecular weight of 1100.
After the B-type substance is finished, the hyperbranched microcrystalline nucleating agent is synthesized according to the following formula:
the A-class substance (specifically, hydroxy di-p-tert-butyl aluminum benzoate, manufacturer is Shanxi chemical institute), the B-class substance (the prepared hyperbranched polyester of end benzoic acid) and the C-class substance (specifically, ethylene bis-stearamide, manufacturer is Japanese flower king) are mixed, and the weight ratio of the A-class substance to the B-class substance to the C-class substance is 7:1:2. then the ultrasonic treatment is carried out for 5 to 30 minutes to lead each component to be dispersed evenly, and then spray drying is carried out to obtain a spray drying product, thus obtaining the hyperbranched microcrystalline nucleating agent. Wherein the air inlet temperature is 120 ℃ and the air outlet temperature is 80 ℃ in the spray drying process.
Hyperbranched microcrystalline nucleating agent and polypropylene matrix resin (manufacturer: quanzhou petrochemical H3030 resin) prepared by each experimental group and control group are respectively prepared according to the following ratio of 0.1: after being uniformly mixed in a mass ratio of 100, the mixture was melt-extruded and pelletized by a twin-screw extruder at 210℃and a screw speed of 100rpm, and tensile test standard bars were injection molded, and mechanical properties were tested, and the results are shown in Table 1.
Wherein the flexural modulus in Table 1 is determined according to the national standard GB/T9341-2008 method.
Young's modulus is determined by ASTM D638-14.
Experimental groups 1-2
Experimental group 1-2 was identical to experimental group 1-1 except for the following variations: the trimesic acid is replaced by trimellitic anhydride, and the molar ratio of the trimellitic anhydride to the ethylene glycol is adjusted to be 1:1, the addition ratio of 1, 3-bisoxazoline is 5 percent of the mole number of the trimellitic anhydride without adding a catalyst. The weight average molecular weight of the hyperbranched aromatic polyester prepared by measurement is 2900.
Experimental groups 1-3
Experimental group 1-3 was identical to experimental group 1-1 except for the following variations: the trimesic acid is replaced by pyromellitic dianhydride, the ethylene glycol is replaced by glycerin, and the molar ratio of the pyromellitic dianhydride to the glycerin is adjusted to be 1:2, without adding 1, 3-bisoxazoline, the reaction temperature of the first step is adjusted to 40 ℃ for 4 hours, and the reaction temperature of the first step is adjusted to 100 ℃ for 24 hours. The hyperbranched aromatic polyester prepared by measurement has the weight average molecular weight of 6000.
Experimental groups 1 to 4
Experimental group 1-4 was identical to experimental group 1-1 except for the following variations: the trimesic acid is replaced by pyromellitic dianhydride, the reaction temperature of the first step is adjusted to 80 ℃ for 1 hour, and the reaction temperature of the second step is adjusted to 250 ℃ for 1 hour. The weight average molecular weight of the hyperbranched aromatic polyester prepared by measurement is 5000.
Control group 1-1
The contrast group 1-1 is different from the experimental group 1-1 in that the hyperbranched microcrystalline nucleating agent is prepared by spray drying of only the A-type substance and the C-type substance without adding the B-type substance.
Control group 1-2
Control group 1-2 differed from experimental group 1-1 described above in that: directly blending without spray drying to prepare the hyperbranched microcrystalline nucleating agent.
The results are shown in Table 1.
Table 1 results of mechanical property test of each experimental group and control group
As can be seen from table 1:
compared with the control group 1-1 without the B-type substance, the hyperbranched aromatic polyester added in the invention can improve the nucleation effect of the final hyperbranched microcrystalline nucleating agent in the polypropylene matrix resin, and improve the flexural modulus and Young modulus of polypropylene.
Compared with the control group 1-2 without spray drying, the spray drying preparation process of the hyperbranched micro-crystal nucleating agent can enable symbiotic micro-crystal growth between hyperbranched aromatic polyester and organic metal salt to be more complete, promote the nucleation effect of the hyperbranched micro-crystal nucleating agent, and promote the tensile modulus and the flexural modulus of a final experimental spline.
In addition, the final molecular weight of the hyperbranched aromatic polyester prepared in the invention has a certain influence on the nucleation effect of the hyperbranched microcrystalline nucleating agent; the nucleation effect with a molecular weight of about 3000 shows the most excellent effect.
Example 2
Example 2 the effect of adjusting the weight ratio of the three components of the A-class material, the B-class material and the C-class material on the nucleation effect was studied.
Firstly, preparing the benzoic acid-terminated hyperbranched polyester according to the following method:
the molar ratio of the trimesic acid to the glycol is 1:0.5 is added into a reactor, and then toluene sulfonic acid (the molar quantity of which is 10 percent of that of trimesic acid) serving as a catalyst is added, and the mixture is reacted for 1 hour at 80 ℃ under the protection of inert gas nitrogen; then adding 1, 3-bisoxazoline (the molar quantity of which is 20 percent of that of trimesic acid), raising the temperature to 120 ℃, vacuumizing the reaction system, and continuously reacting for 1 hour under the condition of reduced pressure to prepare the hyperbranched aromatic polyester. The hyperbranched aromatic polyester has a weight-average molecular weight of 1100.
After the B-type substance is finished, the hyperbranched microcrystalline nucleating agent is synthesized according to the following formula:
the weight ratios of the A-type substance (specifically, hexahydrophthalic acid sodium salt, manufacturer: american Melikin Co., ltd.), the B-type substance (the hyperbranched polyester of terminal benzoic acid prepared as described above), the C-type substance (specifically, stearamide, manufacturer: japanese flower king) and the C-type substance are shown in Table 2.
The hyperbranched microcrystalline nucleating agent and the polypropylene matrix resin (manufacturer: petrochemical T30S resin) prepared are respectively prepared according to the following ratio of 0.1: after being uniformly mixed in a mass ratio of 100, the mixture was melt-extruded and pelletized by a twin-screw extruder at 210℃and a screw speed of 100rpm, and tensile test standard bars were injection molded, and mechanical properties were tested, and the results are shown in Table 2.
The heat distortion temperature in Table 2 is determined by ASTM D648.
TABLE 2 thermal deformation temperature test results for each of the experimental and control groups
It can be seen from table 2 that the addition of the hyperbranched microcrystalline nucleating agent in different proportions has a greater influence on the final nucleation effect. The ratio of the three components of the experiment group 2-2, the A-type substance, the B-type substance and the C-type substance is 7:1:2 is most effective.
Compared with the control group 2-1 containing only the A-type substance or the control group 2-2 containing only the A-type substance and the C-type substance, the heat distortion temperature of the polypropylene resin containing the hyperbranched microcrystalline nucleating agent is higher, and the hyperbranched microcrystalline nucleating agent composition has excellent nucleating effect in the polypropylene matrix resin. This shows that the hyperbranched polymer is a main reason for improving the heat distortion temperature of the polypropylene matrix resin, improves the dispersion degree of the organic metal salt in the polypropylene, and improves the heat resistance of the polypropylene plastic product.
At the same time, the heat distortion temperatures of the experimental groups 2-1 to 2-5 were higher than those of the untreated experimental groups by the spray drying treatment; control group 2-1 and control group 2-2 did not vary much. This demonstrates that the organic carboxylate and hyperbranched aromatic polyester of the present invention are more prone to forming crystallites, improving nucleation and increasing the heat distortion temperature of the polypropylene matrix resin by spray drying.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (15)
1. The preparation method of the hyperbranched microcrystalline nucleating agent is characterized by comprising the following steps of:
the preparation method comprises the steps of mixing an organic metal salt nucleating agent, hyperbranched aromatic polyester and fatty acid amide, and performing spray drying to obtain the organic metal salt nucleating agent; wherein, contain: 50 to 90 weight parts of organic metal salt nucleating agent, 1 to 50 weight parts of hyperbranched aromatic polyester and 0 to 30 weight parts of fatty acid amide, wherein the weight parts of the fatty acid amide are not 0.
2. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 1, wherein,
the organometallic salt nucleating agent comprises: at least one of a metal monocyclocarboxylate, a metal bicyclocarboxylate and a metal substituted heteroaromatic phosphate;
the monocyclic carboxylic acid metal salt includes: at least one of sodium benzoate, calcium benzoate, sodium phthalate, sodium p-tert-butylbenzoate, aluminum p-tert-butylbenzoate, and hexahydrophthalate metal salt;
the metal salt of a bicyclic carboxylic acid includes: at least one of disodium bicycloheptane dicarboxylate, calcium bicycloheptane dicarboxylate, disodium bicyclooctane dicarboxylate;
the substituted aromatic heterocyclic metal phosphate salts include: at least one of sodium 2,2 '-methylenebis (4, 6-di-tert-butylphenyl) phosphate and basic aluminum 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate.
3. The method for preparing the hyperbranched microcrystalline nucleating agent according to claim 1, wherein the average grain size of the hyperbranched microcrystalline nucleating agent prepared is less than 100 microns.
4. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 3, wherein,
the average grain diameter of the prepared hyperbranched microcrystalline nucleating agent is less than 10 microns.
5. The method for producing a hyperbranched microcrystalline nucleating agent according to claim 1, wherein the hyperbranched aromatic polyester has a weight-average molecular weight ranging from 500 to 6000.
6. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 5, wherein,
the weight average molecular weight of the hyperbranched aromatic polyester is 1000-3000.
7. The method for producing a hyperbranched microcrystalline nucleating agent according to claim 1, wherein the hyperbranched aromatic polyester is a carboxyl-terminated hyperbranched aromatic polyester having a carboxylic acid as a terminal group;
the carboxyl-terminated hyperbranched aromatic polyester is selected from one of benzoic acid-terminated hyperbranched aromatic polyester, phthalic acid-terminated hyperbranched aromatic polyester and terephthalic acid-terminated hyperbranched aromatic polyester.
8. The method for preparing the hyperbranched microcrystalline nucleating agent according to claim 1, wherein the hyperbranched aromatic polyester is obtained by the following method:
(1) Mixing polybasic aromatic carboxylic acid/anhydride and polyhydric alcohol, and reacting for 1-4 hours at 40-120 ℃ under the protection of inert gas and under the condition of catalyst;
(2) Adding bisoxazoline, heating to 100-250 ℃, and continuously reacting for 1-20 hours under vacuum and decompression conditions to obtain the hyperbranched aromatic polyester;
the catalyst is 0-10% of the mole number of the polybasic aromatic carboxylic acid/anhydride;
the bisoxazoline accounts for 0 to 20 percent of the mole number of the polybasic aromatic carboxylic acid/anhydride.
9. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 8, wherein,
the polybasic aromatic carboxylic acid/anhydride is carboxylic aromatic organic matter with carboxyl functionality not lower than 2, and the carboxylic aromatic organic matter is at least one selected from trimesic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride;
the polyalcohol is an alcohol organic matter with hydroxyl functionality not lower than 2, and the alcohol organic matter is at least one selected from ethylene glycol, propylene glycol, butanediol, hexanediol, glycerol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, xylitol and sorbitol;
the catalyst is an ester condensation catalyst, and the ester condensation catalyst is at least one selected from sulfuric acid, toluenesulfonic acid, butyl titanate, dibutyl tin dilaurate, stannous chloride and stannous octoate;
the bisoxazoline is selected from at least one of 2,2'- (1, 3-phenylene) bis (2-oxazoline), 2' -bis (2-oxazoline) and 1, 4-bis (2-oxazolinyl) benzene.
10. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 8, wherein,
the molar ratio of the polyaromatic carboxylic acid/anhydride to the polyol is 1:0.5 to 2.
11. The method for preparing the hyperbranched microcrystalline nucleating agent according to claim 1, wherein the method comprises the following steps:
60 to 80 parts by weight of an organic metal nucleating agent,
1 to 30 parts by weight of hyperbranched aromatic polyester,
5 to 20 parts by weight of fatty acid amide.
12. The method for preparing the hyperbranched microcrystalline nucleating agent according to claim 1, comprising:
(1) Dissolving an organic metal salt nucleating agent, hyperbranched aromatic polyester and fatty acid amide to form a raw material solution;
(2) Carrying out ultrasonic treatment on the raw material solution to obtain a solution with uniform dispersion;
(3) And (3) spray drying the solution obtained in the step (2) in a spray mode to obtain a spray-dried product, and thus the hyperbranched microcrystalline nucleating agent is obtained.
13. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 12, wherein,
the ultrasonic treatment time is 5-30 minutes.
14. The method for preparing hyperbranched microcrystalline nucleating agent according to claim 12, wherein the air inlet temperature of the spray drying is 110 ℃ to 200 ℃ and the air outlet temperature of the spray drying is 0 ℃ to 90 ℃.
15. A method for producing a polyolefin resin, comprising:
mixing a hyperbranched microcrystalline nucleating agent obtained according to the preparation method of the hyperbranched microcrystalline nucleating agent of any one of claims 1 to 14 with a polyolefin matrix resin, and melting.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319576B1 (en) * | 2000-11-20 | 2001-11-20 | The Coca-Cola Company | Method to increase the crystallization rate of polyesters |
| EP1557441A2 (en) * | 2003-12-08 | 2005-07-27 | Peter Dr. Wilharm | Nucleating agent based on hyperbranched polymers |
| CN103044863A (en) * | 2011-10-14 | 2013-04-17 | 中国石油化工股份有限公司 | Plastic composition, preparation method thereof and plastic product thereform |
| CN110760126A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Heat-resistant impact-resistant polypropylene composition and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6673870B2 (en) * | 2002-05-13 | 2004-01-06 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
| EP1680464A1 (en) * | 2003-11-07 | 2006-07-19 | Milliken & Company | Concentrates of saturated bicyclic dicarboxylate salts as polymer nucleation additives and methods of nucleating thermoplastics |
| CN101353421B (en) * | 2008-09-17 | 2010-12-08 | 武汉工程大学 | Polyester type hyperbranched polymer pigment dispersant and preparation thereof |
| CN103497319A (en) * | 2013-08-16 | 2014-01-08 | 立邦工业涂料(上海)有限公司 | Hyper-branched polyester resin pigment dispersant, preparation method and color paste thereof, as well as applications of color paste |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6319576B1 (en) * | 2000-11-20 | 2001-11-20 | The Coca-Cola Company | Method to increase the crystallization rate of polyesters |
| EP1557441A2 (en) * | 2003-12-08 | 2005-07-27 | Peter Dr. Wilharm | Nucleating agent based on hyperbranched polymers |
| CN103044863A (en) * | 2011-10-14 | 2013-04-17 | 中国石油化工股份有限公司 | Plastic composition, preparation method thereof and plastic product thereform |
| CN110760126A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Heat-resistant impact-resistant polypropylene composition and preparation method thereof |
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