CN103467749B - There is the hyperbranched polymer of-C-N-flexible chain structure, its Compositional type solidifying agent and preparation method thereof - Google Patents
There is the hyperbranched polymer of-C-N-flexible chain structure, its Compositional type solidifying agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of hyperbranched polymer, its Compositional type solidifying agent and preparation method thereof with-C-N-flexible chain structure.This hyperbranched polymer carries out polycondensation generation by thanomin and acrylate affixture and core element, and its number-average molecular weight is 1000 ~ 7000, and active end group number is 5 ~ 24; Described core element is the polyol containing two or more hydroxyls; The structural formula of described thanomin and acrylate affixture is:
.High-strength high-toughness epoxy resin curing system of the present invention obtain cured article has intensity, rigidity is high, the advantage of good toughness.Be suitable for the component worked in high performance structures matrix material and alternating hot and cold, ultra-low temperature surroundings.
Description
Technical field
The present invention relates to a kind of hyperbranched polymer, its Compositional type solidifying agent and preparation method thereof.Particularly a kind of hyperbranched polymer, its Compositional type solidifying agent and preparation method thereof with-C-N-flexible chain structure.
Background technology
Epoxy resin is the thermoset macromolecule material that a class has good cementability, electrical insulating property, chemical stability, as the resin matrix of tackiness agent, coating and matrix material etc., is widely used in the fields such as building, mechanical, electric, aerospace.
Epoxy resin must add solidifying agent when using, and be cured reaction under certain condition, generate the product of tridimensional network, just can show various excellent performance, become the macromolecular material with real use value, therefore solidifying agent has the effect with epoxy resin no less important in the application of epoxy resin.The selection of epoxy resin solidifying system is by the decision complete processing of epoxy resin and the application performance of cured article.
Fragility due to epoxy resin limits its range of application, therefore causes the toughening modifying research of epoxy resin and pays close attention to widely.Physical method and chemical process two kinds can be divided into the method for epoxy resin roughening.Wherein, physical method is realized by physical blending between epoxy resin and properties-correcting agent, and physical method generally can reduce the performance such as intensity, thermotolerance of cured article while toughness reinforcing; Chemical process is realized by the epoxy resin of synthesizing new structure or the solidifying agent of novel texture, realized by the change of cured article network structure because chemical process is toughness reinforcing, so can accomplish not reduce the performance such as intensity, thermotolerance even improving cured article while toughness reinforcing, thus obtain high-strength high-toughness epoxy resin curing system.
Because the research and development difficulty of neo-epoxy resin is very large, and to obtain high-performance epoxy resin system by the research and development of Novel curing agent be economically viable method.Hyperbranched polymer (HBPs) has the performances such as low entanglement, high reaction activity, high resolution and low viscosity characteristics, is widely used in the Research on Toughening of epoxy resin.The present invention, by the design preparation of the hyperbranched solidifying agent of flexible chain and the composite usage with aromatic amine epoxy resin curing agent, obtains high-strength high-toughness epoxy resin curing system, is suitable for the fields such as low temperature resistant structured material, shock-resistant matrix material.
Summary of the invention
An object of the present invention is to provide a kind of hyperbranched polymer with-C-N-flexible chain structure.
Two of object of the present invention is to provide the hyperbranched solidifying agent of hyperbranched polymer containing this-C-N-flexible chain structure and imidazoles end group.
Three of object of the present invention is to provide the Compositional type solidifying agent containing this hyperbranched solidifying agent.
Four of object of the present invention is the preparation method providing this Compositional type solidifying agent a kind of.
Hyperbranched polymer has highly branched 3-D solid structure, and end is with numerous functional group, and non-crystallizable between molecule, nothing is wound around, and therefore hyperbranched polymer has the character such as high resolution, low viscosity, extensive chemical reactive behavior.By to the Molecular Structure Design of hyperbranched polymer and terminal group modification, the functional materials of different performance and application can be obtained.
For achieving the above object, the present invention adopts following technical scheme:
A kind of hyperbranched polymer with-C-N-flexible chain structure, it is characterized in that this hyperbranched polymer carries out polycondensation generation by thanomin and acrylate affixture and core element, its number-average molecular weight is 1000 ~ 7000, and active end group number is 5 ~ 24; Described core element is the polyol containing two or more hydroxyls; The structural formula of described thanomin and acrylate affixture is:
.
Above-mentioned core element is the amidated products of TriMethylolPropane(TMP), trolamine, neopentyl glycol or urocanic acid ester affixture and diethanolamine, and its structural formula is:
.
A kind of hyperbranched polymer with-C-N-flexible chain structure, it is characterized in that this hyperbranched polymer be undertaken that transesterification reaction obtains by above-mentioned hyperbranched polymer and urocanic acid ester there is-C-N-flexible chain structure and the hyperbranched polymer containing imidazoles end group, the weight of contained imidazoles end group accounts for 20% ~ 50% of hyperbranched polymer molecule amount; Described urocanic acid ester is that imidazole derivative and methyl acrylate carry out addition reaction and obtain, described imidazole derivative is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethyl imidazol(e), 2,4-methylimidazole or 4-methylimidazole.
A kind of Compositional type solidifying agent, is characterized in that this Compositional type solidifying agent is had-C-N-flexible chain structure by above-mentioned and obtained by the mass ratio of 1:1 ~ 1:3 is composite containing the hyperbranched polymer of imidazoles end group and aromatic amine curing agent; Described aromatic amine epoxy curing agent is: mphenylenediamine MPD, diaminodiphenylmethane DDM, 4,4 '-diamino-3,3 '-diethyl ditane DEDDM, diamino diphenyl sulfone DDS or diethyl toluene diamine DETDA.
Prepare a method for above-mentioned Compositional type solidifying agent, it is characterized in that the concrete steps of the method are:
A. after diethanolamine and methyl acrylate being pressed the mixed in molar ratio for 1:1 ~ 1:1.5, stirring at room temperature reaction is dissolved completely to diethanolamine, be warming up to 50 DEG C ~ 80 DEG C stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain light yellow clear liquid, i.e. diethanolamine acrylate affixture;
B. core element is heated to 100 DEG C ~ 150 DEG C, the diethanolamine acrylate affixture of step a gained is slowly added wherein in batches, then stirring reaction 4 ~ 7 hours, the methyl alcohol that decompression removing simultaneously generates, namely cooling is had the hyperbranched polymer of-C-N-flexible chain structure;
C. imidazole derivative and methyl acrylate are pressed the mixed in molar ratio of 1:1 ~ 1:1.5, be stirred to imidazole derivative in 50 DEG C to dissolve completely, be warming up to 80 DEG C ~ 120 DEG C stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture;
D. by the hyperbranched polymer with-C-N-flexible chain structure of step b gained and the urocanic acid ester affixture of step c gained by after the mixed in molar ratio of hydroxyl and urocanic acid ester 1:0.8 ~ 1:1.1, add the KOH of catalyst levels as catalyzer, be warming up to 140 DEG C ~ 160 DEG C fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools namely deep yellow cream solid has-C-N-flexible chain structure and the hyperbranched polymer containing imidazoles end group;
There is-C-N-flexible chain structure and namely obtain Compositional type solidifying agent after fully mixing with aromatic amine epoxy curing agent containing the hyperbranched polymer of imidazoles end group e. by steps d gained.
Because-C-N-flexible chain structure end imidazolyl hyper-branched polyester has-C-N-flexible chain structure and hyperbranched three-dimensional geometrical structure, give the toughness reinforcing performance that solidifying agent is outstanding; Simultaneously due to the imidazoles terminal group content very high (weight of contained imidazoles end group accounts for 20% ~ 50% of flexible hyper-branched polyester molecular weight) of this hyperbranched solidifying agent, give the reactive behavior that solidifying agent is higher; And aromatic amine epoxy resin curing agent is owing to having phenyl ring stiff molecule chain structure and good reactive behavior, give intensity and the thermotolerance of solidification object height; Therefore, this hyperbranched solidifying agent and aromatic amine epoxy resin curing agent composite after, achieve the activeness and quietness to epoxy resin, thus obtain high-strength high-toughness epoxy resin curing system.In use, solidifying agent of the present invention mixes with the ratio of epoxy resin in 20:80 ~ 40:60.
Compared with the existing technology, high-strength high-toughness epoxy resin curing system of the present invention obtain cured article has intensity, rigidity is high, the advantage of good toughness.Be suitable for the component worked in high performance structures matrix material and alternating hot and cold, ultra-low temperature surroundings.The present invention designs the hyperbranched solidifying agent having prepared a kind of-C-N-flexible chain structure and imidazoles end group, has toughness reinforcing and feature that is high reaction activity, by the composite usage with aromatic amine epoxy curing agent, obtains high-strength high-toughness epoxy resin curing system.
Accompanying drawing explanation
Fig. 1 is reaction formula and the structural formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (C) of the embodiment of the present invention 1.
Fig. 2 is reaction formula and the structural formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (E) of the embodiment of the present invention 2.
Fig. 3 is reaction formula and the structural formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (J) of the embodiment of the present invention 3.
Fig. 4 is reaction formula and the structural formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (K) of the embodiment of the present invention 4.
Embodiment
illustrate content of the present invention below, but be not limited to the scope of embodiment.
embodiment one:the concrete steps of the present embodiment are:
The preparation of 1.-C-N-flexible chain structure superbrnaching end-hydroxy polyester:
A. the preparation of diethanolamine acrylate affixture: get diethanolamine 1mol and methyl acrylate 1.2mol is placed in there-necked flask, stirring at room temperature reaction is to diethanolamine dissolves completely, be warming up to 50 DEG C of stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain light yellow clear liquid, i.e. diethanolamine acrylate affixture.
The preparation of b.-C-N-flexible chain structure superbrnaching end-hydroxy polyester: get 1mol TriMethylolPropane(TMP) and be placed in there-necked flask, oil bath is heated to 140 DEG C, the diethanolamine acrylate affixture of 9mol step a gained is added wherein in batches, control feed rate slowly, added in 3 hours, then stirring reaction 5 hours, the methyl alcohol that decompression removing simultaneously generates.Cool to obtain thick pale yellow shape liquid, namely end group number is-C-N-flexible chain structure superbrnaching end-hydroxy polyester (C) of 12.System acid number is lower than 20mgKOH/g.The reaction formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (C) and structural formula, refer to Fig. 1.
The preparation of 2.-C-N-flexible chain structure end imidazolyl hyper-branched polyester:
C. the preparation of urocanic acid ester affixture: get 2-ethyl imidazol(e) 1mol and methyl acrylate 1.2mol is placed in there-necked flask, 50 DEG C of stirring reactions are to 2-ethyl imidazol(e) dissolves completely, be warming up to 80 DEG C of stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture.
The preparation of d.-C-N-flexible chain structure end imidazolyl hyper-branched polyester: the urocanic acid ester affixture of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (C) and 6mol step c gained of getting 1mol step b gained is placed in there-necked flask, add the KOH of 0.05% of reactant gross weight as catalyzer, be warming up to 140 DEG C of fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools to obtain the deep yellow cream solid i.e.-C-N-flexible chain structure end imidazolyl hyper-branched polyester of 12 imidazoles end groups.
3. the preparation of activeness and quietness type epoxy curing agent: mix after the ratio of-C-N-flexible chain structure end imidazolyl hyper-branched polyester of steps d gained and aromatic amine curing agent DEDDM 1:2 is in mass ratio heated to 90 DEG C respectively, cooling obtains light yellow cream solid product, i.e. activeness and quietness type epoxy curing agent.
4. the preparation of high-strength high-toughness epoxy resin curing system: by the activeness and quietness solidifying agent of step 3 gained and bisphenol A type epoxy resin E-51 in mass ratio 30:70 carry out composite, obtain high-strength high-toughness epoxy resin curing system, Solidified enzyme is in table 1.
embodiment two:the concrete steps of the present embodiment are:
The preparation of 1.-C-N-flexible chain structure superbrnaching end-hydroxy polyester: get 1mol trolamine and be placed in there-necked flask, oil bath is heated to 140 DEG C, the diethanolamine acrylate affixture of 21mol embodiment one step a gained is added wherein in batches, control feed rate slowly, added in 7 hours, then stirring reaction 5 hours, the methyl alcohol that decompression removing simultaneously generates.Cool to obtain thick pale yellow shape liquid, namely end group number is-C-N-flexible chain structure superbrnaching end-hydroxy polyester (E) of 24.System acid number is lower than 20mgKOH/g.The reaction formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (E) and structural formula, refer to Fig. 2.
The preparation of 2.-C-N-flexible chain structure end imidazolyl hyper-branched polyester:
A. the preparation of urocanic acid ester affixture: get 2-phenylimidazole 1mol and methyl acrylate 1.2mol is placed in there-necked flask, 50 DEG C of stirring reactions are to 2-phenylimidazole dissolves completely, be warming up to 80 DEG C of stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture.
The preparation of b.-C-N-flexible chain structure end imidazolyl hyper-branched polyester: the urocanic acid ester affixture of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (E) and 24mol step a gained of getting 1mol step 1 gained is placed in there-necked flask, add the KOH of 0.05% of reactant gross weight as catalyzer, be warming up to 140 DEG C of fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools to obtain the deep yellow cream solid i.e.-C-N-flexible chain structure end imidazolyl hyper-branched polyester of 24 imidazoles end groups.
3. the preparation of activeness and quietness type epoxy curing agent: mix after the ratio of-C-N-flexible chain structure end imidazolyl hyper-branched polyester of step b gained and aromatic amine curing agent DETDA 1:1 is in mass ratio heated to 90 DEG C respectively, cooling obtains light yellow viscous liquid product, i.e. activeness and quietness type epoxy curing agent.
4. the preparation of high-strength high-toughness epoxy resin curing system: by the activeness and quietness solidifying agent of step 3 gained and bisphenol f type epoxy resin 830 in mass ratio 40:60 carry out composite, obtain high-strength high-toughness epoxy resin curing system, Solidified enzyme is in table 1.
embodiment three:the concrete steps of the present embodiment are:
The preparation of 1.-C-N-flexible chain structure superbrnaching end-hydroxy polyester: get 1mol neopentyl glycol and be placed in there-necked flask, oil bath is heated to 140 DEG C, the diethanolamine acrylate affixture of 6mol embodiment one step a gained is added wherein in batches, control feed rate slowly, added in 2 hours, then stirring reaction 5 hours, the methyl alcohol that decompression removing simultaneously generates.Cool to obtain thick pale yellow shape liquid, namely end group number is-C-N-flexible chain structure superbrnaching end-hydroxy polyester (J) of 8.System acid number is lower than 20mgKOH/g.The reaction formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (J) and structural formula, refer to Fig. 3.
The preparation of 2.-C-N-flexible chain structure end imidazolyl hyper-branched polyester:
A. the preparation of urocanic acid ester affixture: get 2-ethyl-4-methylimidazole 1mol and methyl acrylate 1.2mol is placed in there-necked flask, 50 DEG C of stirring reactions are to 2-ethyl-4-methylimidazole dissolves completely, be warming up to 80 DEG C of stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture.
The preparation of b.-C-N-flexible chain structure end imidazolyl hyper-branched polyester: the urocanic acid ester affixture of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (J) and 8mol step a gained of getting 1mol step 1 gained is placed in there-necked flask, add the KOH of 0.05% of reactant gross weight as catalyzer, be warming up to 140 DEG C of fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools to obtain the deep yellow cream solid i.e.-C-N-flexible chain structure end imidazolyl hyper-branched polyester of 8 imidazoles end groups.
3. the preparation of activeness and quietness type epoxy curing agent: mix after the ratio of-C-N-flexible chain structure end imidazolyl hyper-branched polyester of step b gained and aromatic amine curing agent MPD 1:2 is in mass ratio heated to 90 DEG C respectively, cooling obtains faint yellow cream solid product, i.e. activeness and quietness type epoxy curing agent.
4. the preparation of high-strength high-toughness epoxy resin curing system: by the activeness and quietness solidifying agent of step 3 gained and bisphenol f type epoxy resin 830 in mass ratio 25:75 carry out composite, obtain high-strength high-toughness epoxy resin curing system, Solidified enzyme is in table 1.
embodiment four:the concrete steps of the present embodiment are:
The preparation of 1.-C-N-flexible chain structure superbrnaching end-hydroxy polyester:
A. the preparation of urocanic acid ester affixture: get glyoxal ethyline 1mol and methyl acrylate 1.2mol is placed in there-necked flask, 50 DEG C of stirring reactions are to glyoxal ethyline dissolves completely, be warming up to 80 DEG C of stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture.
B. the preparation of the amidated products of urocanic acid ester affixture and diethanolamine: urocanic acid ester affixture and the 1mol diethanolamine of getting 1mol step a gained are placed in there-necked flask, oil bath is heated to 100 DEG C and is stirred to fusing, react 3 hours, the methyl alcohol that decompression removing simultaneously generates.Cool to obtain thick pale yellow shape liquid and product.
The preparation of c.-C-N-flexible chain structure superbrnaching end-hydroxy polyester: the amidated products of the urocanic acid ester affixture and diethanolamine of getting 1mol step b gained is placed in there-necked flask, oil bath is heated to 140 DEG C, the diethanolamine acrylate affixture of 2mol embodiment one step a gained is added wherein in batches, control feed rate slowly, added in 2 hours, then stirring reaction 5 hours, the methyl alcohol that decompression removing simultaneously generates.Cool to obtain thick pale yellow shape liquid, namely end group number is-C-N-flexible chain structure superbrnaching end-hydroxy polyester (K) of 4.System acid number is lower than 20mgKOH/g.The reaction formula of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (K) and structural formula, refer to Fig. 4.
The preparation of 2.-C-N-flexible chain structure end imidazolyl hyper-branched polyester: the urocanic acid ester affixture of-C-N-flexible chain structure superbrnaching end-hydroxy polyester (K) and 4mol step a gained of getting 1mol step 1 gained is placed in there-necked flask and adds the KOH of 0.05% of reactant gross weight as catalyzer, be warming up to 140 DEG C of fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools to obtain the deep yellow cream solid i.e.-C-N-flexible chain structure end imidazolyl hyper-branched polyester of 5 imidazoles end groups.
3. the preparation of activeness and quietness type epoxy curing agent: mix after the ratio of-C-N-flexible chain structure end imidazolyl hyper-branched polyester of step 2 gained and aromatic amine curing agent DDM 1:3 is in mass ratio heated to 90 DEG C respectively, cooling obtains faint yellow cream solid product, i.e. activeness and quietness type epoxy curing agent.
4. the preparation of high-strength high-toughness epoxy resin curing system: by the activeness and quietness solidifying agent of step 3 gained and bisphenol A type epoxy resin E-44 in mass ratio 20:80 carry out composite, obtain high-strength high-toughness epoxy resin curing system, Solidified enzyme is in table 1.
embodiment five:the concrete steps of the present embodiment are:
1. mix the preparation of aromatic amine curing agent: DETDA, DDM are heated to 90 DEG C respectively, then mix in the ratio of 1:1, after cooling, obtain thick liquid.
2. the preparation of activeness and quietness type epoxy curing agent: under the mixing aromatic amine curing agent normal temperature obtained with the present embodiment step 1 by the-C-N-flexible chain structure end imidazolyl hyper-branched polyester of embodiment four step 2 gained, the ratio of 1:3 mixes in mass ratio, obtain faint yellow viscous product, i.e. activeness and quietness type epoxy curing agent.
4. the preparation of high-strength high-toughness epoxy resin curing system: by the activeness and quietness solidifying agent of step 3 gained and bisphenol A type epoxy resin E-44 in mass ratio 20:80 carry out composite, obtain high-strength high-toughness epoxy resin curing system, Solidified enzyme is in table 1.
embodiment six:epoxy resin cured product performance test methods: curing system is poured in silica gel mould preheated in advance, puts into 90 DEG C, baking oven and solidifies 2h, then at 120 DEG C of aftertreatment 2h.Obtain test standard batten.Tensile property is tested: use the WDW3020 type micro-control electronic universal tester test newly being tested company limited's manufacture by Changchun according to standard GB/T2568-1995.Bending property is tested: use the WDW3020 type micro-control electronic universal tester test newly being tested company limited's manufacture by Changchun according to standard GB/T9341-2008.Test result is in table 1.
Note: the consisting of of 830 resins/isophorone diamine curing system in table 1: 100:25
As can be seen from Table 1, high-strength high-toughness epoxy resin curing system of the present invention has excellent mechanical property, and the mechanical property of cured article is more excellent compared with similar curing system, has the feature of high-strength and high ductility.
Claims (4)
1. one kind has the hyperbranched polymer of-C-N-flexible chain structure, it is characterized in that hyperbranched polymer that this has-C-N-flexible chain structure be undertaken that transesterification reaction obtains by hyperbranched polymer A and urocanic acid ester there is-C-N-flexible chain structure and the hyperbranched polymer containing imidazoles end group, the weight of contained imidazoles end group accounts for 20% ~ 50% of hyperbranched polymer molecule amount; Described urocanic acid ester is that imidazole derivative and methyl acrylate carry out addition reaction and obtain, described imidazole derivative is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethyl imidazol(e), 2,4-methylimidazole or 4-methylimidazole; Described hyperbranched polymer A carries out polycondensation generation by thanomin and acrylate affixture and core element, and its number-average molecular weight is 1000 ~ 7000, and active end group number is 5 ~ 24; Described core element is the polyol containing two or more hydroxyls; The structural formula of described thanomin and acrylate affixture is:
.
2. the hyperbranched polymer with-C-N-flexible chain structure according to claim 1, it is characterized in that described core element is the amidated products of TriMethylolPropane(TMP), trolamine, neopentyl glycol or urocanic acid ester affixture and diethanolamine, its structural formula is:
.
3. a Compositional type solidifying agent, is characterized in that this Compositional type solidifying agent is obtained by the mass ratio of 1:1 ~ 1:3 is composite by the hyperbranched polymer of-C-N-of having flexible chain structure according to claim 1 and aromatic amine curing agent; Described aromatic amine epoxy curing agent is: mphenylenediamine MPD, diaminodiphenylmethane DDM, 4,4 '-diamino-3,3 '-diethyl ditane DEDDM, diamino diphenyl sulfone DDS or diethyl toluene diamine DETDA.
4. prepare the method for Compositional type solidifying agent according to claim 3, it is characterized in that the concrete steps of the method are:
A. after diethanolamine and methyl acrylate being pressed the mixed in molar ratio for 1:1 ~ 1:1.5, stirring at room temperature reaction is dissolved completely to diethanolamine, be warming up to 50 DEG C ~ 80 DEG C stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain light yellow clear liquid, i.e. diethanolamine acrylate affixture;
B. core element is heated to 100 DEG C ~ 150 DEG C, the diethanolamine acrylate affixture of step a gained is slowly added wherein in batches, then stirring reaction 4 ~ 7 hours, the methyl alcohol that decompression removing simultaneously generates, namely cooling is had the hyperbranched polymer A of-C-N-flexible chain structure;
C. imidazole derivative and methyl acrylate are pressed the mixed in molar ratio of 1:1 ~ 1:1.5, be stirred to imidazole derivative in 50 DEG C to dissolve completely, be warming up to 80 DEG C ~ 120 DEG C stirring reactions again after 2 hours, decompression steams excessive methyl acrylate, obtain faint yellow cream solid, i.e. urocanic acid ester affixture;
D. by the hyperbranched polymer A with-C-N-flexible chain structure of step b gained and the urocanic acid ester affixture of step c gained by after the mixed in molar ratio of hydroxyl and urocanic acid ester 1:0.8 ~ 1:1.1, add the KOH of catalyst levels as catalyzer, be warming up to 140 DEG C ~ 160 DEG C fusings to stir, decompression simultaneously steams methyl alcohol to quality no longer changes, cools namely deep yellow cream solid has-C-N-flexible chain structure and the hyperbranched polymer containing imidazoles end group;
There is-C-N-flexible chain structure and namely obtain Compositional type solidifying agent after fully mixing with aromatic amine epoxy curing agent containing the hyperbranched polymer of imidazoles end group e. by steps d gained.
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| CN106832219B (en) * | 2017-01-22 | 2019-01-29 | 中南民族大学 | A kind of containing phosphorus-nitrogen halogen-free flame-retardant hyperbranched epoxy resin and preparation method thereof |
| CN110330638B (en) * | 2019-07-09 | 2022-02-01 | 陕西科技大学 | Epoxy-terminated hyperbranched polymer, and preparation method and application thereof |
| CN114672035A (en) * | 2022-03-18 | 2022-06-28 | 湖南工业大学 | Hyperbranched polymer delustering agent and preparation method and application thereof |
| CN114773578B (en) * | 2022-03-24 | 2023-12-26 | 武汉工程大学 | Epoxy resin co-curing agent, preparation method and application thereof |
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