CN101235133B - End-vinyl ultra-branching resin and its synthesis method and use - Google Patents
End-vinyl ultra-branching resin and its synthesis method and use Download PDFInfo
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Abstract
The invention relates to a terminated ethenyl hyper branched resin, a preparation method and an application. The preparation method comprises reacting alicyclic or aromatic acid anhydride compound with at least 3 of functionality with diatomic alcohol B to prepare AB<n> monomer, while n>=2, using polycarboxylic compound or acid anhydride compound as core to process polyesterification with AB<n> monomer to prepare terminated carboxyl hyper branched resin, using vinylation to modify the hyper branched resin terminated with carboxyl into terminated vinyl hyper branched resin which is terminated with vinyl, wherein the number average relative molecular mass of the terminated vinyl hyper branched resin is 1000-10000. The terminated vinyl hyper branched resin can be used as auxiliary curing agent to improve the high-low temperature mechanical character of EPT rubber (EPDM)/polypropylene (PP) thermoplastic elastomer composite material and improve the flowability of the material at fusion state.
Description
Technical field
The invention belongs to chemical field and field of compound material, the present invention relates to a kind of end-vinyl ultra-branching resin and preparation method and use, is the preparation that novel cocuring agent is used for terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material with end-vinyl ultra-branching resin.
Background technology
Terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastomer composite study starts from twentieth century sixties, only adopts method with above-mentioned two kinds of material simple blend to be prepared at that time.W.K.Fisher in 1973 have proposed the notion of partial vulcanization, and U.S. Uniroyal company has released passes through the blending thermoplastic elastomer that the dynamic vulcanization effect prepares partially crosslinked terpolymer EP rubber and polypropylene (EPDM/PP).The method of the usefulness dynamic full vulcanizations such as A.Y.Coran of U.S. Monsanto Company in 1981 has prepared the Thermoplastic Elastomer, Olefinic of the full cross-linking type of commodity Santoprent by name, be also referred to as thermoplastic elastic vulcanized rubber (TPV), and TPV has been carried out systematic research work.
The vulcanization system that is used to prepare dynamic full vulcanization EPDM/PP commixed type TPV mainly contains sulphur/promotor, superoxide/additional crosslinker and resol/additional crosslinker three classes.
Adopt the organic peroxide sulfuration system, its cross-link bond is the C-C key, and the ageing-resistant performance of vulcanized rubber is good, compression set is little.But mechanical property is relatively poor, and especially tear strength is relatively poor, and can produce the materials such as methyl phenyl ketone that the smell is awful in the course of processing.In addition, superoxide easily causes PP cracking or crosslinked, and the fragility of the matrix material of formation is increased, and can not satisfy service requirements.
Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences has designed a kind of " second third glue/polypropylene thermoplastic elastomer and preparation method thereof " (publication number 85102222A), adopt dicumyl peroxide, diamyl methyne four thiuramsulfides to make linking agent, it can make rubber full cross-linked, again plastics are not had obviously crosslinked and Degradation, metals such as copper are not had corrosive nature yet.This product can be used for field of cables, exists smell man-hour but add, and the flowability of product is poor.
Hubei University's chemistry adopts the maleimide cross-linking system with Materials Academy, and zinc oxide, stearic acid are made activator, and crosslinking time weak point, sulfuration odorlessness, flowability advantage is preferably arranged, but the complete processing complexity, to the requirement height of forcing machine.
Adopt sulfur sulfide system, the tensile strength of material, elasticity are improved, but vulcanization rate is slow, the finished product outward appearance is not good, and lacks good processing flowability.
Adopt phenolic resin vulcanization system, the tensile strength of material, elasticity are improved; Promoting agent is a zinc oxide, if adopt SnCl
2, the cross-linking density of may command rubber phase.Though poor mechanical property with the resol sulfurized EPDM/PP composite materials property matrix material more prepared than sulfur sulfide system, but the mechanical property than the matrix material for preparing with peroxide vulcanizing system is good, and the carbon black reinforcement is to increase its tensile strength.Adopt phenolic resin vulcanization system, the processing fluidity of product is than peroxide vulcanizing system difference, but better than sulfur sulfide system, and can utilize extending oil to improve its processing fluidity.
Except that peroxide vulcanizing system, the true qualities of the thermoplastic elastomer of all the other two kinds of vulcanization system preparations are yellow or deep yellow, so be unfavorable for the painted of material.And the flowing property of the prepared thermoplastic elastomer high-temperature fusion body of three kinds of vulcanization systems is not fine.With respect to not adding the PP that EPDM carries out modification, its melting index has reduction significantly.Make the use range of material be very limited like this, be unfavorable for being injection molded into large-scale parts and thin wall component.Material flowability can very poorly also increase the energy consumption in the course of processing simultaneously, reduces working efficiency.
Summary of the invention
In order to overcome the above-mentioned shortcoming that EPDM/PP thermoplastic elastomer composite materials property is bad, the high-temperature fusion liquid flowability can differ from of utilizing peroxide vulcanizing system sulfuration preparation, the invention provides a kind of end-vinyl ultra-branching resin and preparation method and use, is the preparation that novel cocuring agent is used for terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material with end-vinyl ultra-branching resin.When utilizing end-vinyl ultra-branching resin, not only can improve the mechanical property and the low-temperature performance of this class matrix material, can also improve the flowing property of such matrix material high-temperature fusion body simultaneously as the cocuring agent of EPDM/PP thermoplastic elastomer composite material.The number average relative molecular mass of this hyperbranched resin (
) be controlled at 1000～10000.
This end-vinyl ultra-branching resin adopts that to have functionality be that alicyclic or aromatic anhydride compd A more than 3 becomes AB with dibasic alcohol B prepared in reaction
nMonomer, n 〉=2; With multi-carboxy compound or anhydride compound is nuclear, by with AB
nMonomeric polyesterification reaction is prepared into the hyperbranched resin that end group is a carboxyl; Be that to become end group be the end-vinyl ultra-branching resin of vinyl for the hyperbranched resin modification of carboxyl by vinylation reaction with end group again; And the number average relative molecular mass of end-vinyl ultra-branching resin
Be controlled at 1000～10000.
The synthetic method of end-vinyl ultra-branching resin, carry out according to the following steps: a, to have functionality and be 3 alicyclic or aromatic anhydride compd A and dibasic alcohol B, maybe will to have functionality be alicyclic or aromatic anhydride compd A more than 3, dibasic alcohol B and water, add and be equipped with in the reactor of organic solvent, the add-on of dibasic alcohol is controlled at anhydride compound and diatomic alcohol compounds mol ratio at 1: 1～2: 1, the add-on of water is controlled at anhydride compound and water mol ratio at 1: 0～1: 2, temperature of reaction is controlled at 60～180 ℃, reaction times was controlled at 0.5～5 hour, was prepared into AB
nMonomer, n 〉=2; B, in reactor, add multi-carboxy compound or anhydride compound and organic solvent again, with AB
nMonomer carries out polyesterification reaction, control multi-carboxy compound or anhydride compound and AB
nMonomer mole ratio was at 1: 3～1: 12, and temperature of reaction is controlled at 80～250 ℃, and the reaction times was controlled at 1～10 hour, and getting end group is the hyperbranched resin of carboxyl; C, in reactor, add vinylated raw material again, the mole number that adds vinylated raw material equals the mole number of carboxyl in the hyperbranched resin molecule that end group is a carboxyl, temperature of reaction is controlled at 50～150 ℃, and the reaction times was controlled at 1～5 hour, and getting end group is the hyperbranched resin of vinyl; D, c step reaction is prepared into end-vinyl ultra-branching resin by the vacuum removal organic solvent after finishing again, the temperature of vacuum desolventizing is controlled at 60～150 ℃, vacuum degree control is at 0.01～0.095MPa, and wherein a, the total consumption of organic solvent in two steps of b are 10%～100% of anhydride compound and diatomic alcohol compounds gross weight.
The aromatic anhydride compd A of described functionality more than 3 is trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride; Alicyclic anhydride compound is a hexahydro-trimellitic acid 1,2-anhydride just 1,2,4-tricarboxylic basic ring hexane or hexahydro-pyromellitic acid dianhydride just 1,2,4,5-tetracarboxylic hexanaphthene.
Described dibasic alcohol B is an ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, a condensed ethandiol, 1,4-hydroxymethyl-cyclohexane or 1,4-xylenediol.
Described multi-carboxy compound is phthalic acid, terephthalic acid, m-phthalic acid, a trimellitic acid just 1,3,4-three carboxyl benzene or pyromellitic acid just 1,2,4,5-tetracarboxylic benzene, described anhydride compound are Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride.
Described organic solvent is benzene,toluene,xylene, methylethylketone, methyl ethyl diketone, tetrahydrofuran (THF), dioxane, N, N
/-dimethyl formamide, N, N
/-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), ethyl acetate are or/and butylacetate.
When described b went on foot polyesterification reaction, can also add: tosic acid, tetrabutyl titanate, calcium oxide, plumbous oxide or antimony oxide catalyst, catalyst consumption were controlled at 0.1%～5% of anhydride compound and diatomic alcohol compounds gross weight.
Described vinylated raw material is vinylformic acid Racemic glycidol fat or methyl propenoic acid glycidyl fat.
Described end-vinyl ultra-branching resin is used to prepare the purposes of terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material.
The preparation method of terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material, with the peralcohol is the vulcanization crosslinking agent, with above-mentioned end-vinyl ultra-branching resin is cocuring agent, the consumption of its end-vinyl ultra-branching resin is the 0.001-20% of PP and EPDM total resin weight, the preparation of employing dynamic vulcanization technology, described peralcohol is dicumyl peroxide (DCP), 1, two (t-butylperoxy diisopropylbenzyl) benzene (P-F) of 4-, 1, two (t-butylperoxy diisopropylbenzyl) benzene (BIPB) of 3-, 4,4 '-bis(t-butylperoxy) n-butyl pentanoate (V), 2,5-dimethyl-2,5-two (t-butylperoxy) hexane (DBPMH), 2,5-dimethyl-2,5-two (t-butylperoxy)-3-hexin (3-hexin) or 1,1-di-t-butyl peroxy-3,3,5-trimethoxy hexamethylene ring (3M); Employed polypropylene (PP) comprises the isotatic polypropylene and the PPR resin of various melting index, employed terpolymer EP rubber (EPDM) comprises the ethylidene norbornene terpolymer EP rubber (ENB-EPDM) and the dicyclopentadiene terpolymer EP rubber (DCPD-EPDM) of the various trades mark, can be equipped with conventional ethylene-propylene rubber(EPR) and polyacrylic auxiliary agent in preparation, it comprises the promoting agent and the scorch retarder of oxidation inhibitor, pigment, anti-aging agent, tenderizer, superoxide.
Utilize end-vinyl ultra-branching resin provided by the present invention to be cocuring agent, not only can improve the cryogenic mechanics performance of terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material, but also can improve the flowability under this class material molten state.
Description of drawings
Fig. 1 is the high temperature rheology graphic representation of EPDM/PP thermoplastic elastomer.
Annotate: test condition is as follows: Harpro high temperature capillary rheometer, capillary diameter are 1.27mm, length-to-diameter ratio=20/1, and extrusion temperature is 180 ℃.
Embodiment
Below be embodiment of the present invention, but the specific embodiments that actual implementation content proposed by the invention is not only limited among the embodiment to be proposed.
One, end-vinyl ultra-branching resin is synthetic:
Embodiment 1:
Agitator is being housed, reflux exchanger, in the reactor of water trap and thermometer, add the 218g pyromellitic acid dianhydride, 18g water, 90g butyleneglycol and 30mL solvent dimethyl formamide (DMF), open and stir, be warmed up to 100 ℃, after reacting 5 hours under this temperature, add 54.5 g pyromellitic acid, 10 gram tosic acid and 200mL dimethylbenzene, be warmed up to the refluxing xylene temperature and under this temperature, react complete until the water sepn of polycondensation formation, after reaction finishes, the glycidyl acrylate that adds 384g again, continuation is after reacting 3 hours under the refluxing xylene temperature, in vacuum tightness is 0.095MPa, decompression and solvent recovery under 100 ℃ of conditions obtains a kind of light yellow thick end-vinyl ultra-branching polyester.
Embodiment 2:
Agitator is being housed, reflux exchanger, in the reactor of water trap and thermometer, add the 191g trimellitic acid 1,2-anhydride, 62g ethylene glycol and 20ml solvent dimethyl sulfoxide (DMSO) (DMSO), open and stir, be warmed up to 120 ℃, after reacting 2 hours under this temperature, add the 19g trimellitic acid, 10 gram weisspiessglanz and 200mL dimethylbenzene, be warmed up to the refluxing xylene temperature and under this temperature, react complete until the water sepn of condensation reaction formation, after reaction finishes, the glycidyl acrylate that adds 256g again, continuation is after reacting 1 hour under the refluxing xylene temperature, in vacuum tightness is 0.09MPa, decompression and solvent recovery under 100 ℃ of conditions obtains a kind of light yellow solid end-vinyl ultra-branching polyester.
Embodiment 3:
Agitator is being housed, reflux exchanger, in the reactor of water trap and thermometer, add 178g hexahydro-trimellitic acid 1,2-anhydride, 106g one condensed ethandiol and 40ml solvent dioxane, open and stir, be warmed up to 150 ℃, after reacting 1.5 hours under this temperature, add 19g trimellitic acid and 200mL toluene, be warmed up to the refluxing toluene temperature and under this temperature, react complete until the water sepn of condensation reaction formation, after reaction finishes, the glycidyl acrylate that adds 256g again, continuation is after reacting 5 hours under the refluxing toluene temperature, in vacuum tightness is 0.095MPa, decompression and solvent recovery under 100 ℃ of conditions obtains a kind of light yellow thick end-vinyl ultra-branching polyester.
Embodiment 4:
Agitator is being housed, reflux exchanger, in the reactor of water trap and thermometer, add 224g hexahydro-pyromellitic acid dianhydride, 18 gram water and 138g1, the solvent ethyl acetate of 4-xylenediol and 45ml, open and stir, be warmed up to 100 ℃, after reacting 4 hours under this temperature, add 65g trimellitic acid 1,2-anhydride and 200mL toluene, be warmed up to the refluxing toluene temperature and under this temperature, react complete until the water sepn of condensation reaction formation, after reaction finishes, the glycidyl methacrylate that adds 200g again, continuation is after reacting 4 hours under the refluxing toluene temperature, in vacuum tightness is 0.08MPa, decompression and solvent recovery under 100 ℃ of conditions obtains a kind of light yellow solid end-vinyl ultra-branching polyester.
Two, the preparation of EPDM/PP thermoplastic elastic composite material
According to table 1 listed each material and consumption, with polypropylene and terpolymer EP rubber premix 1～3 time, make Preblend, again with Preblend, end-vinyl ultra-branching resin, vulcanizing agent dicumyl peroxide (DCP), cyanacrylate (TAIC), 2, the 6-di-tert-butyl-4-methy phenol be called for short other auxiliary agent such as antioxidant 264 be mixed together add twin screw extruder carry out vulcanization crosslinking and extrude, granulation, extruder temperature is controlled at 185～195 ℃.The pellet of preparation is behind dry 2h under 100 ℃, and secondary is extruded again, granulation, drying.
The prescription that proposes among the prescription that Comparative Examples proposed and the embodiment is similar, but does not add end-vinyl ultra-branching resin.
The enforcement of table 1 EPDM/PP thermoplastic elastic composite material
Each material of example and consumption and each material of comparative example and consumption
| Embodiment | PP | EPDM | End-vinyl ultra-branching resin | DCP | TAIC | Antioxidant 264 |
| 5 | 680g | 120g | 2.4g | 0.6g | 0g | 4g |
| 6 | 680g | 120g | 2.4g | 0.6g | 0g | 4g |
| 7 | 680g | 120g | 4.8g | 0.6g | 1.2g | 4g |
| 8 | 680g | 120g | 4.8g | 0.6g | 1.2g | 4g |
| Comparative example | 680g | 120g | 0g | 0.6g | 2.4g | 4g |
What the end-vinyl ultra-branching resin in the example 5 was used is the end-vinyl ultra-branching resin of the invention process 1 preparation, what the end-vinyl ultra-branching resin in the example 6 was used is the end-vinyl ultra-branching resin of the invention process 2 preparations, what the end-vinyl ultra-branching resin in the example 7 was used is the end-vinyl ultra-branching resin of the invention process 3 preparations, and what the end-vinyl ultra-branching resin in the example 8 was used is the end-vinyl ultra-branching resin of the invention process 4 preparations.
Adopt the mechanical property of the PP/EPDM thermoplastic elastomer sample of above method preparation to list in table 2.Wherein tensile property is pressed the GB/T1040-92 test, and test rate is: 50mm/min; Bending property is pressed the GB/T9341-2000 test; Socle girder impact property under the cold condition is pressed the GB/T1843-1996 test, and sample was placed in-20 ℃ environment after 16 hours, carried out the test of impact property immediately.
The mechanical property of table 2 PP/EPDM thermoplastic elastomer
| Embodiment | Tensile strength (MPa) | Elongation at break (%) | Flexural strength (MPa) | Modulus in flexure (MPa) | Low temperature notched shock strength/-20 ℃ (kJ/m 2) |
| 5678 comparative examples | 18.95 19.68 19.31 18.51 22.21 | 769.14 720.57 540.85 775.57 470.89 | 20.81 20.44 19.59 19.65 21.45 | 820.46 828.88 793.89 826.84 836.47 | 46.9 42.9 40.9 40.9 40.3 |
The data of table 2 show: the elongation at break and the low temperature impact properties of the PP/EPDM thermoplastic elastomer of the present invention's preparation increase substantially, and other mechanical properties decrease is little, can satisfy service requirements.
The high temperature rheology of said sample can be as shown in Figure 1:
As can be seen from Figure 1: the melt viscosity of EPDM/PP thermoplastic elastomer under melt temperature that utilizes method preparation of the present invention is much smaller than comparative example.Therefore the PP/EPDM thermoplastic elastomer that utilizes the present invention to prepare is suitable for processing thin-walled polypropylene articles, as bumper, seat etc.
Claims (8)
1. end-vinyl ultra-branching resin adopts that to have functionality be that alicyclic or aromatic anhydride compd A more than 3 becomes AB with dibasic alcohol B prepared in reaction
nMonomer, n 〉=2; With multi-carboxy compound or anhydride compound is nuclear, by with AB
nMonomeric polyesterification reaction is prepared into the hyperbranched resin that end group is a carboxyl; Be that the hyperbranched resin of carboxyl is modified as the end-vinyl ultra-branching resin that end group is a vinyl by vinylation reaction with end group again; And the number average relative molecular mass (M of end-vinyl ultra-branching resin
n) be controlled at 1000～10000, described multi-carboxy compound is phthalic acid, terephthalic acid, m-phthalic acid, a trimellitic acid just 1,3,4-three carboxyl benzene or pyromellitic acid just 1,2,4,5-tetracarboxylic benzene, described anhydride compound are Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride and pyromellitic acid dianhydride.
2. the synthetic method of end-vinyl ultra-branching resin according to claim 1, carry out according to the following steps: a, to have functionality and be 3 alicyclic or aromatic anhydride compd A and dibasic alcohol B, maybe will to have functionality be alicyclic or aromatic anhydride compd A more than 3, dibasic alcohol B and water, add and be equipped with in the reactor of organic solvent, the add-on of dibasic alcohol is controlled at anhydride compound and diatomic alcohol compounds mol ratio at 1: 1～2: 1, the add-on of water is controlled at anhydride compound and water mol ratio at 1: 0～1: 2, temperature of reaction is controlled at 60～180 ℃, reaction times was controlled at 0.5～5 hour, was prepared into AB
nMonomer, n 〉=2; B, in reactor, add multi-carboxy compound or anhydride compound and organic solvent again, with AB
nMonomer carries out polyesterification reaction, control multi-carboxy compound or anhydride compound and AB
nMonomer mole ratio was at 1: 3～1: 12, and temperature of reaction is controlled at 80～250 ℃, and the reaction times was controlled at 1～10 hour, and getting end group is the hyperbranched resin of carboxyl; C, in reactor, add vinylated raw material again, the mole number that adds vinylated raw material equals the mole number of carboxyl in the hyperbranched resin molecule that end group is a carboxyl, temperature of reaction is controlled at 50～150 ℃, and the reaction times was controlled at 1～5 hour, and getting end group is the hyperbranched resin of vinyl; D, c step reaction is prepared into end-vinyl ultra-branching resin by the vacuum removal organic solvent after finishing again, the temperature of vacuum desolventizing is controlled at 60～150 ℃, vacuum degree control is at 0.01～0.095MPa, wherein a, the total consumption of organic solvent in two steps of b are 10%～100% of anhydride compound and diatomic alcohol compounds gross weight, and described vinylated raw material is vinylformic acid Racemic glycidol fat or methyl propenoic acid glycidyl fat.
3. the synthetic method of end-vinyl ultra-branching resin according to claim 2, it is characterized in that: the aromatic anhydride compd A of described functionality more than 3 is trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride; Alicyclic anhydride compound is a hexahydro-trimellitic acid 1,2-anhydride just 1,2, oneself ring of 4-tricarboxylic basic ring or hexahydro-pyromellitic acid dianhydride just 1,2,4,5-tetracarboxylic hexamethylene ring.
4. the synthetic method of end-vinyl ultra-branching resin according to claim 2, it is characterized in that: described dibasic alcohol B is an ethylene glycol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, a condensed ethandiol, 1,4-hydroxymethyl-cyclohexane or 1,4-xylenediol.
5. the synthetic method of end-vinyl ultra-branching resin according to claim 2, it is characterized in that: described organic solvent is benzene,toluene,xylene, methylethylketone, methyl ethyl diketone, tetrahydrofuran (THF), dioxane, N, N
/-dimethyl formamide, N, N
/-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), ethyl acetate are or/and butylacetate.
6. the synthetic method of end-vinyl ultra-branching resin according to claim 2, it is characterized in that: when described b goes on foot polyesterification reaction, also add: tosic acid, tetrabutyl titanate, calcium oxide, plumbous oxide or antimony oxide catalyst, catalyst consumption are controlled at 0.1%～5% of anhydride compound and diatomic alcohol compounds gross weight.
7. end-vinyl ultra-branching resin according to claim 1 is used to prepare the purposes of terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material.
8. the preparation method of terpolymer EP rubber (EPDM)/polypropylene (PP) thermoplastic elastic composite material, it is characterized in that: be the vulcanization crosslinking agent with the peralcohol, with the described end-vinyl ultra-branching resin of claim 1 is cocuring agent, the consumption of its end-vinyl ultra-branching resin is the 0.001-20% of PP and EPDM total resin weight, adopts the dynamic vulcanization technology preparation.
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| CN105085932B (en) * | 2015-07-10 | 2018-11-16 | 宁波大学 | Hyperbranched graft polymers of polyethylene-and preparation method thereof |
| CN105037706B (en) * | 2015-07-10 | 2017-07-14 | 宁波大学 | A kind of three block polyvinyl dissaving polymer and its production and use |
| CN105038082B (en) * | 2015-08-15 | 2018-09-18 | 无锡市群星线缆有限公司 | A kind of high intensity resists cold ethylene propylene diene rubber and preparation method thereof |
| CN105086325B (en) * | 2015-08-15 | 2019-01-11 | 上海玖开电线电缆有限公司 | A kind of cold resistant cable ethylene propylene rubber insulation material |
| CN109401081B (en) * | 2018-10-31 | 2021-07-23 | 江苏达胜高聚物股份有限公司 | Heat-resistant cable material and preparation method and application thereof |
| CN110885433B (en) * | 2019-05-24 | 2022-07-19 | 武汉金发科技有限公司 | Hyperbranched polyester and synthesis method thereof, and thermoplastic resin composition and preparation method thereof |
| CN110204835B (en) * | 2019-05-24 | 2022-08-16 | 武汉金发科技有限公司 | Toughening agent composition, thermoplastic resin composite material and preparation method thereof |
| CN111592653A (en) * | 2020-04-13 | 2020-08-28 | 浙江大学 | Preparation method of topological elastomer with highly branched structure and low-modulus high elasticity |
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