CN110256660A - A kind of hyper-branched polyester and its synthetic method and a kind of thermoplastic resin composition and preparation method thereof - Google Patents
A kind of hyper-branched polyester and its synthetic method and a kind of 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
- C08G63/02—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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- 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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of hyper-branched polyester and a kind of thermoplastic resin compositions, by weight, including following components: 60-85 parts of thermoplastic resin；End-capping group contains 1-12 parts of hyper-branched polyester of vinyl；End-capping group containing vinyl accounts for the 3%-100% of hyperbranched poly ester terminal sum.Hyper-branched polyester containing vinyl ends is able to ascend the toughness of thermoplastic resin.And, if nano inorganic filler is added, hyper-branched polyester can improve dispersibility of the nano inorganic filler in thermoplastic resin composition, also completely cut off directly contacting for a large amount of nano inorganic fillers and thermoplastic resin, so as to improve and improve the decline of toughness caused by the addition of nano inorganic filler.
Description
Technical field
The present invention relates to technical field of macromolecules, more particularly to a kind of hyper-branched polyester and its synthetic method and a kind of heat
Thermoplastic resin composition and preparation method thereof.
Background technique
Automotive light weight technology is the important directions of automobile industry development, nano inorganic filler is added to increase the intensity of material,
But a large amount of additions of filler can also reduce the toughness of material.The general method for solving toughness decline be to nano inorganic filler into
Row is modified: the nano montmorillonite (MMT) of two-dimensional layered structure can carry out cationic exchange, intercalation and splitting due to piece interlayer
At the characteristic of 1nm sheet layer, it has also become prepare the excellent filler of polymer nanocomposites.However, above-mentioned polypropylene/illiteracy is de-
There are preparation process complexity and the insufficient defect of performance for soil composite material.Moreover, after a large amount of nano montmorillonites are added in polypropylene
It will lead to the decline of toughness, Chinese patent 201410430715.0 discloses a kind of organo montmorillonite and its modified polypropene tree
Rouge wherein handling nano montmorillonite using cetyl trimethylammonium bromide, then compounds cetyl trimethylammonium bromide, epoxy
Resin, isophorone diisocyanate make polypropylene have good toughness, still, will lead in this way ingredient too it is high be unsuitable for it is big
Sizable application.Therefore need to develop new method to improve the toughness of material of nano inorganic filler filling.
Hyperbranched resin has highly branched structure, has a large amount of end group, less winding is between molecule to be not easy
Crystallization has highly dissoluble, low viscosity and higher chemical reactivity.These show that hyperbranched resin in many aspects
Tempting application prospect is shown, as polymer processing aids, the carrier of enzyme, drug corrosion inhibiter, molecular self-assembling, other modifications add
Add agent etc..Chinese patent 201610969753.2 discloses a kind of hyperbranched resin, utilizes bis-phenol A glycidyl ether, benzene front three
End carboxyl super branched resin is prepared in the one-step method reaction of acid and succinic acid under triphenyl phosphine catalyst；Pass through feed ratio
Control, thus it is possible to vary the chain structure and carboxyl end group density of hyperbranched resin can be used for modified epoxy, with asphalt mixtures modified by epoxy resin
Compatibility between rouge is preferable, and peripheral carboxyl can promote the effect of the interface cohesion between hyperbranched resin and epoxy resin, preparation
End carboxyl super branched resin modified epoxy resin composite have excellent mechanical property and low internal stress.Chinese patent Shen
201810903887.3 it please disclose a kind of PP composite material: polypropylene 5-95%；Inorganic filler: 5-60%；Hyperbranched tree
Rouge: 0.1-3%；Antioxidant: 0.1-0.8%；Antistatic agent 0.1-1.0%.Wherein, hyperbranched resin is hyper-branched polyester, hyperbranched
Polyphosphate or hyperbranched unsaturated double-bond resin, the purpose that hyperbranched resin is added are to improve rigidity and extension at break
Rate.Chinese patent application 201810227583.X discloses a kind of antistatic polypropylene composition, including following parts by weight of component:
40~80 parts of acrylic resin and as 1~8 part of hyperbranched polyethyleneimine of antistatic agent；By adding hyperbranched polyethylene
Imines is antistatic agent, and a large amount of amino is contained in hyperbranched polyethyleneimine end, and amino absorbs the moisture in air and conductive,
To reduce surface resistivity, electrostatic is eliminated.But blocking modification is not carried out to hyper-branched polyester, improve thermoplastic resin
Toughness, the especially toughness of nano inorganic filler filling thermoplastic resin composition.
Summary of the invention
The object of the present invention is to provide a kind of hyper-branched polyesters, are blocked using the end-capping group containing vinyl
Processing, the hyper-branched polyester that end-capping group contains vinyl can not only promote the toughness of thermoplastic resin, and can improve
Because the addition of inorganic nano-filler leads to the decline of toughness.
Another object of the present invention is to provide a kind of hyper-branched polyesters for being added to above-mentioned end-capping group and containing vinyl
Thermoplas tic resin composite and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of hyper-branched polyester, the end-capping group containing vinyl accounts for hyperbranched poly ester terminal sum in the hyper-branched polyester
3%-100%.
The END CAPPED GROUP for the hyper-branched polyester that the present invention selects contains vinyl, is because containing the hyperbranched of vinyl ends
Polyester is heated in screw rod, squeezes out, the autogenous crosslinking of shearing meeting, so that hyper-branched polyester is formed net distribution, to improve thermoplasticity
The toughness of resin combination；If joined nano inorganic filler, nano inorganic can be promoted to fill out under less additional amount
The dispersibility of material and it is separated with thermoplastic resin matrix, so improve because the addition of nano inorganic filler cause it is tough
The reduction of property.
The end-capping group hyper-branched polyester that contains vinyl that the embodiment of the present invention is selected is that trimellitic anhydride is core, partially
The AB of benzenetricarboxylic acid acid anhydride and ethylene glycol synthesis2Type monomer is branch, by the hyper-branched polyester of the capping reagent sealing end containing vinyl.
The synthetic method of above-mentioned hyper-branched polyester, comprising the following steps: the esterification contracting between trimellitic anhydride and ethylene glycol
Poly- reaction synthesis AB2Type monomer, then it is anti-using esterifying polycondensation of the trimellitic anhydride between core and trimellitic anhydride and ethylene glycol
The AB that should be synthesized2Monomer reaction obtains uncapped hyper-branched polyester, reuses reagent containing ethenyl blocking and is blocked
Group contains the hyper-branched polyester of vinyl.
Uncapped hyper-branched polyester has many branches, and there are two carboxyl, two carboxyl energy for tool on the phenyl ring of the branch end of the chain
Enough react well with modifying agent connects other groups for containing vinyl.
Preferably, the end-capping group contains the molecular weight 2000-5000 of the hyper-branched polyester of vinyl.Synthesis process
In mainly control the molecule of the hyper-branched polyester that end-capping group contains vinyl by controlling amount and the reaction time of monomer
Amount, if molecular weight is too small, coat, isolation effect it is bad, not can effectively improve tough caused by the addition of nano inorganic filler
Property decline.It tangles if molecular weight is too high, between molecule excessively, also tangles excessively during melt extrusion, be easy to cause and receive
The dispersion effect of rice inorganic filler is bad, increases preparation difficulty.End-capping group contains the molecular weight of the hyper-branched polyester of vinyl
The value range of generally one normal distribution, according to the of different sizes of its different distribution of synthetic method.Control molecular weight
Peak value can be improved the effect of thermoplas tic resin composite's impact strength reduction in the range of preferred 2000-5000
Fruit.
The synthetic method for the hyper-branched polyester that the specific end-capping group of the embodiment of the present invention contains vinyl can be such that
AB2The synthesis of monomer: the amount of the substances such as addition into the three-necked flask with blender, thermometer and reflux condenser
Trimellitic anhydride, ethylene glycol, a certain amount of solvent and a small amount of catalyst, start stirring, are heated to 120 DEG C of reaction 3h, so
Vacuum distillation removes solvent afterwards, obtains a kind of faint yellow solid, i.e. AB2Monomer.
End-capping group contains the synthesis of the hyper-branched polyester of vinyl: the present invention is using divergent method synthesis end with carboxyl
Hyper-branched polyester.The trimellitic anhydride of metering is added into the three-necked flask with blender, water segregator and reflux condenser,
AB2 Monomer, appropriate solvent and a small amount of catalyst, start stirring, are heated to 120 DEG C and maintain the reflux for 3h, until separating
Stop reaction after learning the water of metering, then vacuum distillation removes solvent, obtains uncapped hyper-branched polyester dispersion solution.
It is acrylamido that the present invention, which tests the used END CAPPED GROUP containing vinyl, is also possible to other and contains ethylene
The group of base.The reaction reagent for the acrylamido that the present invention uses is 2- acrylamide-2-methylpro panesulfonic acid.
Uncapped hyper-branched polyester carries out termination process；By uncapped hyper-branched polyester, 2- acrylamido -2- first
Base propane sulfonic acid and the addition of appropriate tetrahydrofuran are placed in the reaction flask of magnetic stir bar, are stirred at room temperature and are made it dissolve homogeneously；It instills
The pyridine catalyst of metering reacts at room temperature certain time.Then precipitating is filtered out, filtrate is through the water-soluble liquid precipitate of petroleum ether, multiple water
The hyper-branched polyester product that end-capping group contains vinyl is made after washing and being dried in vacuo.
The ratio of the capping reagent containing vinyl and uncapped hyper-branched polyester be can control to adjust containing ethylene
The end-capping group of base accounts for hyperbranched poly ester terminal sum.As end group is constantly blocked, steric hindrance be will increase, and will increase envelope
The difficulty of reaction is held, and the end group containing vinyl of itself is easy to happen intramolecular crosslinking, and the increase of toughness is caused to be slowed down
The performance even reduced instead.
Preferably, the end-capping group containing vinyl accounts for hyperbranched poly ester terminal sum in the hyper-branched polyester
15%-70%。
The synthesis of other synthetic methods also can be used in uncapped hyper-branched polyester, and synthon is also possible to other objects
Matter, as bis-phenol A glycidyl ether, benzenetricarboxylic acid and succinic acid synthesize.Uncapped hyper-branched polyester either hyperbranched poly
Phosphate, hyper-branched polyester containing unsaturated double-bond etc..
End-capping group contains the hyper-branched polyester characterizing method of vinyl are as follows: FTIR test prepares poling with acetone as solvent
Then weak solution is coated in bromination sylvite on piece and forms film, measure on Perkin-Elmer Fourier infrared spectrograph.It finds
Vinyl absorption peak investigates whether the end-capping group containing vinyl is reacted connects.
A kind of thermoplastic resin composition, by weight, including following components:
60-85 parts of thermoplastic resin；
End-capping group contains 1-12 parts of hyper-branched polyester of vinyl；
End-capping group containing vinyl accounts for the 3%-100% of hyperbranched poly ester terminal sum.
The thermoplastic resin in polypropylene, polyethylene, polyamide, polyphenylene sulfide, polycarbonate at least one
Kind；The polypropylene is selected from least one of homopolypropylene, copolymer polypropylene；The polyethylene is poly- selected from low-density
At least one of ethylene, high density polyethylene (HDPE), linear low density polyethylene；The polyamide be selected from fatty polyamide,
At least one of aromatic polyamide, semiaromatic polyamide composition.
It by weight, further include 0-30 parts of nano inorganic filler；The nano inorganic filler, which is selected from nanometer and covers, to be taken off
At least one of soil, nano talc, nanometer calcium carbonate.Preferably, the interlamellar spacing of the nano montmorillonite is 1.5-
5nm, radius-thickness ratio 20-200.The inorganic filler of other nanometer particle size ranks can also be selected, is added to promote thermoplastic resin
Intensity.
If adding nano inorganic filler, the hyper-branched polyester that end-capping group contains vinyl can be attached to nano inorganic and fill out
Expect to disperse nano inorganic filler uniformly in thermoplastic resin composition, and coat a large amount of nano inorganic on surface
Filler, to improve influence of the addition to toughness of nano inorganic filler.
It by weight, further include 0-10 parts of auxiliary agent；The auxiliary agent is selected from antioxidant, UV resistant agent, lubricant
At least one of.
Other compatilizers or toughener can also be suitably added in the present invention, as SEBS grafted maleic anhydride, polypropylene connect
Branch maleic anhydride, Research of Grafting Malaic Anhydride Onto Polyethylene etc..
The lubricant is in stearate series lubricant agent, fatty acid lubricant, stearate series lubricant agent
It is at least one；The stearate series lubricant agent is selected from least one of calcium stearate, magnesium stearate, zinc stearate；Institute
The fatty acid lubricant stated is selected from least one of fatty acid, derivative of fatty acid, aliphatic ester；The stearate
Series lubricant agent is selected from least one of pentaerythritol stearate；Preferably, the lubricant is lubricated selected from fatty acid
At least one of agent, stearate series lubricant agent.
The UV resistant agent is selected from benzo three and frustrates class ultraviolet absorber, dibenzoic acid class ultraviolet absorber, HALS class
At least one of compound.
The antioxidant is the alkyl of organic phosphite, alkylated monohydric phenol or polyphenol, polyphenol and diene
Change reaction product, butylation product, the alkylated hydroquinones, hydroxylated thio two of paracresol or bicyclopentadiene
Phenyl ethers, alkylidene-bis-phenol, benzyl compounds or polyol ester kind antioxidant.Specifically, the embodiment of the present invention use it is anti-
Oxygen agent is the compounding of common antioxidant 1010 and irgasfos 168, be also possible to other types antioxidant exclusive use or
Compounding.
The preparation method of above-mentioned thermoplastic resin composition, comprising the following steps:
A thermoplastic resin, end-capping group) are contained into the hyper-branched polyester of vinyl, nano inorganic filler in high speed according to the proportion
It is mixed in mixing machine；
B extruder) is added to be kneaded, extrusion screw rod draw ratio is 40-48:1, and 90-120 DEG C of 1st area, 2-5 are pressed in extruder temperature setting
180-200 DEG C of area, 200-230 DEG C of other areas, while double vacuum systems (vacuum degree >=0.06MPa) are opened on extruding machine barrel,
Extruding pelletization obtains thermoplastic resin composition.
The invention has the following beneficial effects:
The present invention improves material by the hyper-branched polyester of end-capping group of the addition containing vinyl in thermoplastic resin composition
The toughness of material.
In thermoplastic resin is commonly modified, thermoplastic resin can add a large amount of nano inorganic fillers and improve thermoplasticity
The intensity of resin combination, but the degradation of toughness can be brought in this way.The hyperbranched poly that END CAPPED GROUP contains vinyl is added
Ester is sheared in screw rod and autogenous crosslinking occurs for high temperature, promotes nano inorganic filler dispersion performance in the material and will be big
Amount nano inorganic filler is separated with thermoplastic resin matrix, improves toughness caused by the addition because of nano inorganic filler
Decline.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
Raw material of the present invention is as follows, but is not only restricted to the following raw material:
Polypropylene: middle petrochemical industry, EP548R, copolymer polypropylene；
Polyethylene: high density polyethylene (HDPE), DMDA8008；
Polyamide: PA66, EP-158；
End-capping group contains the hyper-branched polyester A of vinyl: self-control, the esterifying polycondensation reaction between trimellitic anhydride and ethylene glycol
Synthesize AB2Type monomer, then synthesis is reacted using esterifying polycondensation of the trimellitic anhydride between core and trimellitic anhydride and ethylene glycol
AB2Monomer reaction obtains uncapped hyper-branched polyester, reuses 2- acrylamide-2-methylpro panesulfonic acid as sealing end examination
Agent sealing end；The molecular weight that end-capping group contains the hyper-branched polyester A of vinyl is 3500-3700, and acrylamide fiduciary point is hyperbranched
About the 31% of polyester end groups sum；
End-capping group contains the hyper-branched polyester B of vinyl: self-control contains the hyper-branched polyester A's of vinyl with end-capping group
Difference is, molecular weight 5500-6000, about the 31% of acrylamide fiduciary point hyper-branched polyester end group sum；
End-capping group contains the hyper-branched polyester C of vinyl: self-control contains the hyper-branched polyester A's of vinyl with end-capping group
Difference is, molecular weight 3500-3800, about the 78% of acrylamide fiduciary point hyper-branched polyester end group sum；
End-capping group contains the hyper-branched polyester D of vinyl: self-control contains the hyper-branched polyester A's of vinyl with end-capping group
Difference is, molecular weight 3300-3600, about the 1.5% of acrylamide fiduciary point hyper-branched polyester end group sum；
Uncapped hyper-branched polyester: self-control, the esterifying polycondensation reaction synthesis AB between trimellitic anhydride and ethylene glycol2Type list
Body, then the AB synthesized is reacted using esterifying polycondensation of the trimellitic anhydride between core and trimellitic anhydride and ethylene glycol2Monomer is anti-
It should obtain uncapped hyper-branched polyester；Molecular weight 3600-3700, no END CAPPED GROUP；
Nano montmorillonite: interlamellar spacing 1.5-5nm, radius-thickness ratio 20-200；
Antioxidant: antioxidant 1010: irgasfos 168=1:1 compounding；
Lubricant: fatty acid ester type emollients.
Other raw material sources are in commercially available.
The preparation method of embodiment 1-5 and comparative example 1-2 thermoplastic resin composition: it matches according to table 1 by thermoplastic resin
Rouge (polypropylene, polyethylene or polyamide), nano montmorillonite, hyper-branched polyester are (containing vinyl ends sealing end or uncapped
), antioxidant, lubricant mix in a high speed mixer；Extruder is added to be kneaded, extrusion screw rod draw ratio is 40-48:1, is squeezed
90-120 DEG C of 1st area, 180-200 DEG C of the area 2-5,200-230 DEG C of other areas are pressed in out-of-machine temperature setting, while being opened on extruding machine barrel
Double vacuum systems (vacuum degree >=0.06MPa), extruding pelletization obtains thermoplastic resin composition.
Properties detection method:
(1) 23 DEG C of simply supported beam notch impact strength: examination criteria ISO179；
Table 1: embodiment thermoplastic resin composition component proportion (parts by weight) and each the performance test results
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Polypropylene | 70 | 70 | 70 | 70 | 70 | - | - | 70 |
| Polyethylene | - | - | - | - | - | 70 | - | - |
| Polyamide | - | - | - | - | - | - | 70 | - |
| Nano montmorillonite | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| End-capping group contains the hyper-branched polyester A of vinyl | 1 | 3 | 5 | 10 | - | 3 | 3 | - |
| End-capping group contains the hyper-branched polyester B of vinyl | - | - | - | - | 3 | - | - | - |
| End-capping group contains the hyper-branched polyester C of vinyl | - | - | - | - | - | - | - | 3 |
| Antioxidant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 23 DEG C of simply supported beam notch impact strengths, KJ/m2 | 14 | 22 | 28 | 35 | 20 | 9 | 10 | 20 |
Table 2: comparative example thermoplastic resin composition component proportion (parts by weight) and each the performance test results
| 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 |
| End-capping group contains the hyper-branched polyester D of vinyl | - | - | 3 | - | - |
| Uncapped hyper-branched polyester | - | 3 | - | - | - |
| Antioxidant | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Lubricant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 23 DEG C of simply supported beam notch impact strengths, KJ/m2 | 8 | 10 | 13 | 5 | 6 |
From above table as can be seen that preferred end-capping group contains the hyper-branched polyester molecular weight ranges of vinyl, for
The promotion of toughness is larger.Uncapped hyper-branched polyester, due to its do not have vinyl, cannot in screw rod self-crosslinking, because
This promotion very little for toughness.End-capping group contains the hyper-branched polyester C of vinyl, due to the end-capping group containing vinyl
Content is too small, very limited for the improvement of toughness.From embodiment 2 and embodiment 8 as can be seen that when acrylamide fiduciary point is hyperbranched
Polyester end groups sum is more than to not only increase synthesis difficulty, and the castering action of toughness is started gradually to drop instead after 70%
It is low.
Claims (11)
1. a kind of hyper-branched polyester, which is characterized in that the end-capping group in the hyper-branched polyester containing vinyl accounts for over-expense
Change the 3%-100% of polyester end groups sum.
2. hyper-branched polyester according to claim 1, which is characterized in that the end-capping group contains the over-expense of vinyl
Changing polyester is the AB that trimellitic anhydride is core, trimellitic anhydride and ethylene glycol synthesis2Type monomer is branch, by containing vinyl
The hyper-branched polyester of capping reagent sealing end.
3. thermoplastic resin composition according to claim 1, which is characterized in that the end-capping group contains vinyl
Hyper-branched polyester molecular weight 2000-5000；End-capping group in the hyper-branched polyester containing vinyl accounts for hyperbranched
The 15%-70% of polyester end groups sum.
4. thermoplastic resin composition according to claim 1-3, which is characterized in that described contains vinyl
End-capping group be acrylamido.
5. the synthetic method of the described in any item hyper-branched polyesters of claim 1-4, which comprises the following steps: partially
Esterifying polycondensation reaction synthesis AB between benzenetricarboxylic acid acid anhydride and ethylene glycol2Type monomer, then using trimellitic anhydride as core and inclined benzene three
The AB of esterifying polycondensation reaction synthesis between formic anhydride and ethylene glycol2Monomer reaction obtains uncapped hyper-branched polyester, reuses
Reagent containing ethenyl blocking blocks to obtain the hyper-branched polyester that end-capping group contains vinyl.
6. a kind of thermoplastic resin composition, which is characterized in that by weight, including following components:
60-85 parts of thermoplastic resin；
End-capping group contains 1-12 parts of hyper-branched polyester of vinyl；
End-capping group containing vinyl accounts for the 3%-100% of hyperbranched poly ester terminal sum.
7. thermoplastic resin composition according to claim 6, which is characterized in that the end-capping group contains vinyl
Hyper-branched polyester be trimellitic anhydride be core, trimellitic anhydride and ethylene glycol synthesis AB2Type monomer is branch, is contained second
The hyper-branched polyester of the capping reagent sealing end of alkenyl.
8. thermoplastic resin composition according to claim 6, which is characterized in that the thermoplastic resin is selected from poly- third
At least one of alkene, polyethylene, polyamide, polyphenylene sulfide, polycarbonate；The polypropylene is selected from homopolypropylene, is total to
At least one of poly- polypropylene；The polyethylene is selected from low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene
At least one of alkene；The polyamide in fatty polyamide, aromatic polyamide, semiaromatic polyamide composition extremely
Few one kind.
9. thermoplastic resin composition according to claim 6, which is characterized in that further include 0-30 parts by weight
Nano inorganic filler；The nano inorganic filler in nano montmorillonite, nano talc, nanometer calcium carbonate at least
It is a kind of.
10. thermoplastic resin composition according to claim 6, which is characterized in that further include 0-10 parts by weight
Auxiliary agent；The auxiliary agent is selected from least one of antioxidant, UV resistant agent, lubricant.
11. the preparation method of thermoplastic resin composition described in any one of claim 10, which comprises the following steps:
A thermoplastic resin, nano inorganic filler, end-capping group) are contained into the hyper-branched polyester of vinyl in high speed according to the proportion
It is mixed in mixing machine；
B extruder) is added to be kneaded, extrusion screw rod draw ratio is 40-48:1, and 90-120 DEG C of 1st area, 2-5 are pressed in extruder temperature setting
180-200 DEG C of area, 200-230 DEG C of other areas, while double vacuum systems (vacuum degree >=0.06MPa) are opened on extruding machine barrel,
Extruding pelletization obtains thermoplastic resin composition.
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| CN110643138A (en) * | 2019-09-26 | 2020-01-03 | 广东圆融新材料有限公司 | Modified flame-retardant ABS material and preparation method thereof |
| CN111560141A (en) * | 2020-04-18 | 2020-08-21 | 嘉兴市韶华塑胶新材料有限公司 | Antistatic high-impact polypropylene mine car bearing end cover and preparation method thereof |
| CN112574392A (en) * | 2020-12-14 | 2021-03-30 | 武汉金发科技有限公司 | Application and preparation method of novel hyperbranched polyester chain extender |
| CN112608585A (en) * | 2020-12-10 | 2021-04-06 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
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| CN110643138A (en) * | 2019-09-26 | 2020-01-03 | 广东圆融新材料有限公司 | Modified flame-retardant ABS material and preparation method thereof |
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| CN112608585A (en) * | 2020-12-10 | 2021-04-06 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN112608585B (en) * | 2020-12-10 | 2022-12-30 | 海隆石油产品技术服务（上海）有限公司 | High-filling low-cost biodegradable composite material and preparation method thereof |
| CN112574392A (en) * | 2020-12-14 | 2021-03-30 | 武汉金发科技有限公司 | Application and preparation method of novel hyperbranched polyester chain extender |
| CN114276614A (en) * | 2021-12-24 | 2022-04-05 | 易宝（福建）高分子材料股份公司 | Grafting crosslinking agent for EPDM-PP foaming material and preparation method and application thereof |
| CN114409999A (en) * | 2021-12-31 | 2022-04-29 | 金发科技股份有限公司 | Polypropylene composition and preparation method thereof |
| CN114539667A (en) * | 2022-02-15 | 2022-05-27 | 武汉金发科技有限公司 | Polypropylene composition with lasting antibacterial effect and preparation method and application thereof |
| CN114539667B (en) * | 2022-02-15 | 2023-05-09 | 武汉金发科技有限公司 | Polypropylene composition with lasting antibacterial effect and preparation method and application thereof |
| WO2023174060A3 (en) * | 2022-03-17 | 2023-11-09 | 金发科技股份有限公司 | Non-spray resin, and preparation method and use therefor |
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Application publication date: 20190920 |