CN110885433A - Hyperbranched polyester and synthesis method thereof, and thermoplastic resin composition and preparation method thereof - Google Patents
Hyperbranched polyester and synthesis method thereof, and thermoplastic resin composition and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention discloses hyperbranched polyester and a thermoplastic resin composition, which comprise the following components in parts by weight: 60-85 parts of thermoplastic resin; 1-12 parts of hyperbranched polyester with end groups containing vinyl; the end capping groups containing vinyl account for 3 to 100 percent of the total number of the terminal groups of the hyperbranched polyester. The hyperbranched polyester containing the vinyl end group can improve the toughness of the thermoplastic resin. Moreover, if the nano inorganic filler is added, the hyperbranched polyester can improve the dispersibility of the nano inorganic filler in the thermoplastic resin composition and also isolate a large amount of the nano inorganic filler from being in direct contact with the thermoplastic resin, thereby improving and increasing the reduction of toughness caused by the addition of the nano inorganic filler.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to hyperbranched polyester and a synthesis method thereof, and a thermoplastic resin composition and a preparation method thereof.
Background
The light weight of the automobile is an important direction for the development of the automobile industry, the nano inorganic filler is added to increase the strength of the material, but the toughness of the material is also reduced by adding a large amount of the filler. The general solution to the toughness reduction is to modify the nano inorganic filler: the nano montmorillonite (MMT) with two-dimensional layered structure becomes an excellent filler for preparing polymer nano composite material due to the characteristic that the interlayer can be subjected to cation exchange, intercalation and interlayer stripping to form a 1nm thick layer. However, the polypropylene/montmorillonite composite material has the defects of complex preparation process and insufficient performance. Moreover, the toughness of polypropylene is reduced after a large amount of nano montmorillonite is added, and Chinese patent No. 201410430715.0 discloses an organic montmorillonite and its modified polypropylene resin, wherein the nano montmorillonite is treated with cetyl trimethyl ammonium bromide, and then compounded with cetyl trimethyl ammonium bromide, epoxy resin and isophorone diisocyanate to make the polypropylene have good toughness, but the components are too high to be suitable for large-scale application. Therefore, it is necessary to develop a new method for improving the toughness of the nano inorganic filler filled material.
The hyperbranched resin has a highly branched structure, a large number of end groups, less entanglement among molecules so as to be difficult to crystallize, high solubility, low viscosity and higher chemical reaction activity. The hyperbranched resin has attractive application prospect in many aspects, such as polymer processing aids, enzyme carriers, drug corrosion inhibitors, molecular self-assembly, other modified additives and the like. Chinese patent 201610969753.2 discloses a hyperbranched resin, which is prepared by one-step reaction of bisphenol A glycidyl ether, benzenetricarboxylic acid and succinic acid under the catalysis of triphenylphosphine; through the control of the feeding ratio, the chain structure and the carboxyl-terminated density of the hyperbranched resin can be changed, the hyperbranched resin can be used for modifying epoxy resin, the compatibility between the hyperbranched resin and the epoxy resin is better, the interface bonding effect between the hyperbranched resin and the epoxy resin can be improved by peripheral carboxyl, and the prepared carboxyl-terminated hyperbranched resin modified epoxy resin compound has excellent mechanical property and low internal stress. Chinese patent application 201810903887.3 discloses a polypropylene composite material: 5-95% of polypropylene; inorganic filler: 5 to 60 percent; hyperbranched resin: 0.1-3%; antioxidant: 0.1 to 0.8 percent; 0.1 to 1.0 percent of antistatic agent. The hyperbranched resin is hyperbranched polyester, hyperbranched polyphosphate or hyperbranched unsaturated double-bond resin, and the purpose of adding the hyperbranched resin is to improve rigidity and elongation at break. Chinese patent application 201810227583.X discloses an antistatic polypropylene composition, which comprises the following components in parts by weight: 40-80 parts of polypropylene resin and 1-8 parts of hyperbranched polyethyleneimine serving as an antistatic agent; hyperbranched polyethyleneimine is added as an antistatic agent, the tail end of the hyperbranched polyethyleneimine contains a large amount of amino groups, and the amino groups absorb moisture in air to conduct electricity, so that the surface resistivity is reduced, and static electricity is eliminated. However, the hyperbranched polyester is not subjected to end-capping modification, so that the toughness of the thermoplastic resin, especially the toughness of the thermoplastic resin composition filled with the nano inorganic filler, is improved.
Disclosure of Invention
The invention aims to provide hyperbranched polyester, wherein the end capping treatment is carried out by using an end capping group containing vinyl, and the hyperbranched polyester with the end capping group containing vinyl can not only improve the toughness of thermoplastic resin, but also improve the reduction of the toughness caused by the addition of inorganic nano filler.
Another object of the present invention is to provide a thermoplastic resin composite material to which the hyperbranched polyester having a vinyl group as a terminal capping group is added, and a method for preparing the same.
The invention is realized by the following technical scheme:
the hyperbranched polyester comprises 3-100% of end groups of the hyperbranched polyester, wherein the end groups containing vinyl groups.
The end-capping group of the selected hyperbranched polyester contains vinyl, and the hyperbranched polyester containing the vinyl end group can be subjected to self-generated crosslinking through heating, extrusion and shearing in a screw, so that the hyperbranched polyester forms net distribution to improve the toughness of the thermoplastic resin composition; if the nano inorganic filler is added, the dispersibility of the nano inorganic filler can be promoted and the nano inorganic filler can be separated from the thermoplastic resin matrix under a small adding amount, so that the reduction of the toughness caused by the addition of the nano inorganic filler can be improved.
The hyperbranched polyester with the end-capping group containing vinyl selected in the embodiment of the invention is AB synthesized by using trimellitic anhydride as a core and trimellitic anhydride and ethylene glycol2The type monomer is branched and hyperbranched polyester terminated by a vinyl-containing end-capping reagent.
The synthesis method of the hyperbranched polyester comprises the following steps: AB is synthesized by esterification polycondensation reaction between trimellitic anhydride and ethylene glycol2A monomer, which is prepared by using trimellitic anhydride as a core and reacting trimellitic anhydride and ethylene glycolAB synthesized by esterification polycondensation reaction of2The monomer reacts to obtain non-terminated hyperbranched polyester, and then the terminated hyperbranched polyester with the terminated group containing vinyl is obtained by using a vinyl-containing terminated reagent.
The non-terminated hyperbranched polyester has a plurality of branched chains, the benzene ring at the end of the branched chain has two carboxyl groups, and the two carboxyl groups can well react with a modifying reagent to be connected with other vinyl-containing groups.
Preferably, the molecular weight of the hyperbranched polyester with the end capping group containing vinyl is 2000-5000. The molecular weight of the hyperbranched polyester with the end-capping group containing vinyl is mainly controlled by controlling the amount of the monomer and the reaction time in the synthesis process, if the molecular weight is too small, the coating and isolating effects are not good, and the toughness reduction caused by the addition of the nano inorganic filler cannot be effectively improved. If the molecular weight is too high, molecules are excessively entangled, and the molecules are also excessively entangled in the melt extrusion process, so that the dispersing effect of the nano inorganic filler is poor, and the preparation difficulty is increased. The molecular weight of the hyperbranched polyester with the end capping group containing vinyl is generally within a normal distribution range, and the distribution range is different according to different synthesis methods. Controlling the peak value of the molecular weight within the preferable range of 2000-.
The specific synthesis method of the hyperbranched polyester with the end capping group containing vinyl in the embodiment of the invention can be as follows:
AB2and (3) synthesis of monomers: adding trimellitic anhydride, ethylene glycol, a certain amount of solvent and a small amount of catalyst into a three-neck flask with a stirrer, a thermometer and a reflux condenser, stirring, heating to 120 ℃ for reaction for 3h, and distilling under reduced pressure to remove the solvent to obtain a light yellow solid, namely AB2A monomer.
Synthesizing hyperbranched polyester with vinyl-containing end groups: the invention adopts a divergent method to synthesize hyperbranched polyester with carboxyl at the tail end. A three-neck flask with stirrer, water separator and reflux condenser is charged with a metered amount of trimellitic anhydride, AB2Monomer, proper amount of solvent and small amountAnd (3) starting stirring the catalyst, heating to 120 ℃, keeping refluxing for 3 hours, stopping the reaction until stoichiometric water is separated out, and then distilling under reduced pressure to remove the solvent to obtain the non-terminated hyperbranched polyester dispersion solution.
The vinyl-containing terminal capping group used in the test of the present invention is an acrylamide group, and may be another vinyl-containing group. The acrylamide-based reaction reagent used in the invention is 2-acrylamido-2-methylpropanesulfonic acid.
Carrying out end capping treatment on the non-end capped hyperbranched polyester; adding the non-terminated hyperbranched polyester, 2-acrylamide-2-methylpropanesulfonic acid and a proper amount of tetrahydrofuran into a reaction bottle with a magnetic stirring bar, and stirring at room temperature to dissolve the hyperbranched polyester, the 2-acrylamide-2-methylpropanesulfonic acid and the tetrahydrofuran to form a homogeneous phase; and (3) dropwise adding a metered pyridine catalyst, and reacting for a certain time at room temperature. Then filtering out the precipitate, precipitating the filtrate by petroleum ether aqueous solution, washing for many times and drying in vacuum to prepare the hyperbranched polyester product with the end-capping group containing vinyl.
The ratio of the end-capping reagent containing vinyl groups to the uncapped hyperbranched polyester can be controlled to adjust the total number of end-groups of the hyperbranched polyester that are occupied by end-capping groups containing vinyl groups. With the continuous blocking of the end group, the steric hindrance will increase, the difficulty of the blocking reaction will increase, and the self end group containing vinyl will easily generate intramolecular cross-linking, resulting in the performance of the toughness increase slow down or even decrease.
Preferably, the terminal groups containing vinyl in the hyperbranched polyester account for 15 to 70 percent of the total number of terminal groups of the hyperbranched polyester.
The non-terminated hyperbranched polyester can also be synthesized by other synthesis methods, and the synthesis monomers can also be synthesized by other substances, such as bisphenol A glycidyl ether, benzene tricarboxylic acid and succinic acid. The non-terminated hyperbranched polyester can be hyperbranched polyphosphate ester, hyperbranched polyester containing unsaturated double bonds and the like.
The method for characterizing the hyperbranched polyester with the end group containing the vinyl comprises the following steps: FTIR tests were performed using acetone as a solvent to make a very dilute solution which was then coated onto a potassium bromide salt tablet to form a thin film, as measured on a Perkin-Elmer Fourier Infrared spectrometer. Looking for vinyl absorption peaks to see if the vinyl-containing end-capping group has reacted to the linker.
A thermoplastic resin composition comprises the following components in parts by weight:
60-85 parts of thermoplastic resin;
1-12 parts of hyperbranched polyester with end groups containing vinyl;
the end capping groups containing vinyl account for 3 to 100 percent of the total number of the terminal groups of the hyperbranched polyester.
The thermoplastic resin is selected from at least one of polypropylene, polyethylene, polyamide, polyphenylene sulfide and polycarbonate; the polypropylene is at least one of homopolymerized polypropylene and copolymerized polypropylene; the polyethylene is at least one selected from low density polyethylene, high density polyethylene and linear low density polyethylene; the polyamide is at least one selected from aliphatic polyamide, aromatic polyamide and semi-aromatic polyamide.
0-30 parts of nano inorganic filler; the nano inorganic filler is at least one of nano montmorillonite, nano talcum powder and nano calcium carbonate. Preferably, the interlayer spacing of the nano montmorillonite is 1.5-5nm, and the diameter-thickness ratio is 20-200. Other inorganic fillers with nanometer particle size grade can also be selected and added to improve the strength of the thermoplastic resin.
If the nano inorganic filler is added, the hyperbranched polyester with the end-capping group containing vinyl can be attached to the surface of the nano inorganic filler, so that the nano inorganic filler is uniformly dispersed in the thermoplastic resin composition and is coated with a large amount of nano inorganic filler, thereby improving the influence of the addition of the nano inorganic filler on the toughness.
0-10 parts of auxiliary agent is also included according to the parts by weight; the auxiliary agent is at least one selected from an antioxidant, an anti-ultraviolet agent and a lubricant.
Other compatilizers or toughening agents such as SEBS grafted maleic anhydride, polypropylene grafted maleic anhydride, polyethylene grafted maleic anhydride and the like can also be properly added in the invention.
The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from pentaerythritol stearate; preferably, the lubricant is at least one selected from fatty acid lubricants and stearate lubricants.
The anti-ultraviolet agent is at least one of a benzotriazole ultraviolet absorbent, a dibenzoic acid ultraviolet absorbent and a HALS compound.
The antioxidant is organic phosphite ester, alkylated monophenol or polyhydric phenol, alkylation reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenol, benzyl compounds or polyhydric alcohol esters antioxidant. Specifically, the antioxidant used in the embodiment of the present invention is a combination of the antioxidant 1010 and the antioxidant 168, and may be a single antioxidant or a combination of other antioxidants.
The preparation method of the thermoplastic resin composition comprises the following steps:
A) mixing thermoplastic resin, hyperbranched polyester with end-capping groups containing vinyl and nano inorganic filler in a high-speed mixer according to the proportion;
B) adding the mixture into an extruder for mixing, setting the length-diameter ratio of an extrusion screw to be 40-48:1, setting the temperature of the extruder according to the temperature of 90-120 ℃ in a 1 region, 180-200 ℃ in a 2-5 region and 230 ℃ in other regions, and simultaneously opening a double vacuum system (the vacuum degree is more than or equal to 0.06 MPa) on a screw cylinder of the extruder for extrusion and granulation to obtain the thermoplastic resin composition.
The invention has the following beneficial effects:
the invention improves the toughness of the material by adding the hyperbranched polyester containing the vinyl end capping group into the thermoplastic resin composition.
In the modification commonly used for thermoplastic resins, the thermoplastic resin is added with a large amount of nano inorganic filler to improve the strength of the thermoplastic resin composition, but this brings about a serious decrease in toughness. The hyperbranched polyester with the end-capping group containing vinyl is added to be sheared and subjected to self-generated crosslinking at high temperature in the screw, so that the dispersion performance of the nano inorganic filler in the material is promoted, a large amount of nano inorganic filler is separated from a thermoplastic resin matrix, and the reduction of toughness caused by the addition of the nano inorganic filler is improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials adopted by the invention are as follows, but are not limited to the following raw materials:
polypropylene: mesopetrochemicals, EP548R, co-polypropylene;
polyethylene: high density polyethylene, DMDA 8008;
polyamide: PA66, EP-158;
hyperbranched polyester A with vinyl-containing end groups: self-made AB synthesized by esterification polycondensation reaction between trimellitic anhydride and ethylene glycol2AB synthesized by esterification and polycondensation reaction between type monomer and trimellitic anhydride and ethylene glycol by taking trimellitic anhydride as core2Carrying out monomer reaction to obtain non-terminated hyperbranched polyester, and then using 2-acrylamide-2-methylpropanesulfonic acid as a termination reagent to terminate the terminal; the molecular weight of the hyperbranched polyester A with the end capping group containing vinyl is 3500-3700, and the acrylamide group accounts for about 31 percent of the total number of the end groups of the hyperbranched polyester;
hyperbranched polyester B with end groups containing vinyl groups: self-made, and the difference with the hyperbranched polyester A with the end-capping group containing vinyl is that the molecular weight is 5500-6000, and the acrylamide group accounts for about 31 percent of the total number of the end groups of the hyperbranched polyester;
hyperbranched polyester C with end capping groups containing vinyl groups: self-made, and the difference with the hyperbranched polyester A with the end-capping group containing vinyl is that the molecular weight is 3500-3800, and the acrylamide group accounts for about 78 percent of the total number of the end-groups of the hyperbranched polyester;
hyperbranched polyester with end groups containing vinyl groups D: self-made, and different from the hyperbranched polyester A with the end-capping group containing vinyl, the molecular weight is 3300-3600, and the acrylamide group accounts for about 1.5% of the total number of the end groups of the hyperbranched polyester;
non-end-capped hyperbranched polyester: self-made AB synthesized by esterification polycondensation reaction between trimellitic anhydride and ethylene glycol2AB synthesized by esterification and polycondensation reaction between type monomer and trimellitic anhydride and ethylene glycol by taking trimellitic anhydride as core2Reacting monomers to obtain non-terminated hyperbranched polyester; molecular weight 3600-3700 without end capping group;
nano montmorillonite: the interlayer spacing is 1.5-5nm, and the diameter-thickness ratio is 20-200;
antioxidant: antioxidant 1010: antioxidant 168=1: 1;
lubricant: fatty acid ester lubricants.
Other starting materials are commercially available.
Examples 1 to 5 and comparative examples 1 to 2 thermoplastic resin compositions were prepared by the following methods: mixing thermoplastic resin (polypropylene, polyethylene or polyamide), nano-montmorillonite, hyperbranched polyester (terminated or uncapped with vinyl end group), antioxidant and lubricant in a high-speed mixer according to the mixture ratio in the table 1; adding the mixture into an extruder for mixing, setting the length-diameter ratio of an extrusion screw to be 40-48:1, setting the temperature of the extruder according to the temperature of 90-120 ℃ in a 1 region, 180-200 ℃ in a 2-5 region and 230 ℃ in other regions, and simultaneously opening a double vacuum system (the vacuum degree is more than or equal to 0.06 MPa) on a screw cylinder of the extruder for extrusion and granulation to obtain the thermoplastic resin composition.
The method for detecting the performance comprises the following steps:
(1) impact strength of a gap of a simply supported beam at 23 ℃: the detection standard ISO 179;
table 1: EXAMPLES proportion (parts by weight) of thermoplastic resin composition and results of various property tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| Polypropylene | 70 | 70 | 70 | 70 | 70 | - | - | 70 |
| Polyethylene | - | - | - | - | - | 70 | - | - |
| Polyamide | - | - | - | - | - | - | 70 | - |
| Nano montmorillonite | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Hyperbranched polyester A with end group containing vinyl | 1 | 3 | 5 | 10 | - | 3 | 3 | - |
| Hyperbranched polyester B with terminal group containing vinyl | - | - | - | - | 3 | - | - | - |
| Hyperbranched polyester C with terminal group containing vinyl | - | - | - | - | - | - | - | 3 |
| Antioxidant agent | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 23 ℃ simple beam notch impact strength, KJ/m2 | 14 | 22 | 28 | 35 | 20 | 9 | 10 | 20 |
Table 2: comparative example thermoplastic resin composition component ratios (parts by weight) and results of respective property tests
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Polypropylene | 70 | 70 | 70 | - | - |
| Polyethylene | - | - | - | 70 | - |
| Polyamide | - | - | - | - | 70 |
| Nano montmorillonite | 10 | 10 | 10 | 10 | 10 |
| Hyperbranched polyester D with terminal groups containing vinyl groups | - | - | 3 | - | - |
| Unterminated hyperbranched polyesters | - | 3 | - | - | - |
| Antioxidant agent | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant agent | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 23 ℃ simple beam notch impact strength, KJ/m2 | 8 | 10 | 13 | 5 | 6 |
As can be seen from the above table, the preferred molecular weight range of the hyperbranched polyester containing vinyl groups as end-capping groups is a large improvement in toughness. The non-terminated hyperbranched polyester cannot be crosslinked in a screw by itself because of no vinyl group, so that the improvement on the toughness is small. The hyperbranched polyester C with the end group containing vinyl has limited improvement on toughness because the content of the end group containing vinyl is too small. From example 2 and example 8, it can be seen that, when the total amount of the terminal groups of the hyperbranched polyester is more than 70% of the acrylamide groups, not only the synthesis difficulty is increased, but also the improvement effect on the toughness starts to gradually decrease.
Claims (11)
1. The hyperbranched polyester is characterized in that the end capping groups containing vinyl in the hyperbranched polyester account for 3 to 100 percent of the total number of the end groups of the hyperbranched polyester.
2. The hyperbranched polyester of claim 1, wherein the hyperbranched polyester with the end-capping group containing vinyl group is AB synthesized from trimellitic anhydride as a core, trimellitic anhydride and ethylene glycol2The type monomer is branched and is terminated by a vinyl-containing end-capping reagentA branched polyester.
3. The thermoplastic resin composition as claimed in claim 1, wherein the molecular weight of the hyperbranched polyester having a terminal capping group containing a vinyl group is 2000-5000; the end capping groups containing vinyl in the hyperbranched polyester account for 15 to 70 percent of the total number of the end groups of the hyperbranched polyester.
4. The thermoplastic resin composition of any of claims 1-3, wherein said vinyl-containing end-capping group is an acrylamide group.
5. The method for synthesizing hyperbranched polyester as claimed in any one of claims 1 to 4, comprising the steps of: AB is synthesized by esterification polycondensation reaction between trimellitic anhydride and ethylene glycol2AB synthesized by esterification and polycondensation reaction between type monomer and trimellitic anhydride and ethylene glycol by taking trimellitic anhydride as core2The monomer reacts to obtain non-terminated hyperbranched polyester, and then the terminated hyperbranched polyester with the terminated group containing vinyl is obtained by using a vinyl-containing terminated reagent.
6. A thermoplastic resin composition is characterized by comprising the following components in parts by weight:
60-85 parts of thermoplastic resin;
1-12 parts of hyperbranched polyester with end groups containing vinyl;
the end capping groups containing vinyl account for 3 to 100 percent of the total number of the terminal groups of the hyperbranched polyester.
7. The thermoplastic resin composition of claim 6, wherein said hyperbranched polyester with vinyl groups as end-capping groups is trimellitic anhydride core, and AB is synthesized from trimellitic anhydride and ethylene glycol2The type monomer is branched and hyperbranched polyester terminated by a vinyl-containing end-capping reagent.
8. The thermoplastic resin composition according to claim 6, wherein said thermoplastic resin is at least one selected from the group consisting of polypropylene, polyethylene, polyamide, polyphenylene sulfide, and polycarbonate; the polypropylene is at least one of homopolymerized polypropylene and copolymerized polypropylene; the polyethylene is at least one selected from low density polyethylene, high density polyethylene and linear low density polyethylene; the polyamide is at least one selected from aliphatic polyamide, aromatic polyamide and semi-aromatic polyamide.
9. The thermoplastic resin composition according to claim 6, further comprising 0 to 30 parts by weight of a nano inorganic filler; the nano inorganic filler is at least one of nano montmorillonite, nano talcum powder and nano calcium carbonate.
10. The thermoplastic resin composition according to claim 6, further comprising 0 to 10 parts by weight of an auxiliary; the auxiliary agent is at least one selected from an antioxidant, an anti-ultraviolet agent and a lubricant.
11. A method for producing a thermoplastic resin composition according to claim 10, comprising the steps of:
A) mixing thermoplastic resin, nano inorganic filler and hyperbranched polyester with vinyl-containing end groups in a high-speed mixer according to the proportion;
B) adding the mixture into an extruder for mixing, setting the length-diameter ratio of an extrusion screw to be 40-48:1, setting the temperature of the extruder according to the temperature of 90-120 ℃ in a 1 region, 180-200 ℃ in a 2-5 region and 230 ℃ in other regions, and simultaneously opening a double vacuum system (the vacuum degree is more than or equal to 0.06 MPa) on a screw cylinder of the extruder for extrusion and granulation to obtain the thermoplastic resin composition.
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