CN102070775B - Method for preparing multi-hydroxyl group-containing hyperbranched polyester resin - Google Patents
Method for preparing multi-hydroxyl group-containing hyperbranched polyester resin Download PDFInfo
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- CN102070775B CN102070775B CN 201010545037 CN201010545037A CN102070775B CN 102070775 B CN102070775 B CN 102070775B CN 201010545037 CN201010545037 CN 201010545037 CN 201010545037 A CN201010545037 A CN 201010545037A CN 102070775 B CN102070775 B CN 102070775B
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Abstract
The invention discloses a method for preparing multi-hydroxyl group-containing hyperbranched polyester resin, which comprises the following steps of: reacting epoxy resin or a multi-epoxy group-containing monomer with an alkylol amine structure-containing monomer in a non-protonic solvent under the protection of inert gas according to the molar ratio of 1:(0.7-3.5) at the temperature of between 60 and 260 DEG C for 0.5 to 35 hours; cooling after the epoxy value of the system is reduced to a theoretical value; adding a certain amount of cyclic acid anhydride-containing monomer and single epoxy group-containing monomer, heating and reacting for a certain time to obtain a head product; and precipitating, filtering, separating and drying the head product to obtain the multi-hydroxyl functional group-containing hyperbranched polyester resin. The novel multi-hydroxyl group hyperbranched polyester resin prepared by the method has the advantages of wide raw material sources, low cost, simple process and high controllability; and the obtained polymer contains a great number of hydroxyl functional groups, and has high dissolubility and a broad application prospect.
Description
Technical field
The present invention relates to a kind of hyperbranched, dendritic, vibrin of containing polyhydroxy functional groups.Be mainly used in coating, viscosity modifier, dye well tackiness agent, also be with a wide range of applications in fields such as thermo-setting elastomer, high performance composite and functional film materials.
Background technology
Hyperbranched polymer is classified as Dendritic (dendroid) polymkeric substance, is the new function polymer that grows up the nearly more than ten years.Dendrimer has three-dimensional torispherical structure, a large amount of terminal group and low-viscosity, have unique physicochemical property such as good solubility in solvent.Owing to have highly branched structure, hyperbranched polymer is difficult to crystallization, also twine without chain, thereby solubility property improves greatly.Compare with simple linear polymer, hyperbranched polymer inside has the porous three-dimensional structure, but unique inside nanometer micropore chelating ion, absorption small molecules or the catalytic activity point that reacts as small molecules; The a large amount of active end groups of surface enrichment can obtain desired properties by terminal groups modification.
The initial imagination of hyperbranched polymer is that Flory proposes, and contains the AB of a reactive group A and X another kind of reactive group B
xThe reaction of (X＞2) type monomer process intermolecular condensation can form molecule chain end and remain the highly branched three-dimensional structure of a large amount of unreacted B of functional group and crosslinking reaction does not occur.The structure of hyperbranched polymer uniqueness makes it application all be arranged in a lot of fields.Especially more can show the performance that it is good in the unable scope of taking into account of those conventional linear molecules.
Hyperbranched polymer synthetic need not careful separating-purifying, reduced synthetic cost, and hyperbranched polymer can substitute to a great extent dendritic macromole and uses.Owing to good cost performance is arranged, so hyperbranched polymer just seems more important in the engineering application facet.
Summary of the invention
The object of the invention is to pass through Molecular Structure Design, react synthetic poly-hydroxy Hyperbranched Polyester Resin with wide application prospect with commercial Resins, epoxy, the monomer that contains hydramine and the monomer that contains the monomer of cyclic acid anhydride and contain single epoxy group(ing).
Above-mentioned purpose of the present invention is achieved through the following technical solutions: step (A): component one (Resins, epoxy or contain the monomer of many epoxy group(ing)) is dropped in the reaction flask with component two (monomer that contains pure amine structure), under protection of inert gas, under 60 ℃～260 ℃, in non-protonic solvent, react, reaction times is 0.5～35 hour, obtains containing the polymkeric substance of secondary hydroxyl; Described component one is 1: 0.7～3.5 with component two mol ratios.Step (B): the prepolymer that steps A is obtained is cooled to room temperature, add component three (monomer that contains cyclic acid anhydride) and component four (monomer that contains single epoxy group(ing)), under protection of inert gas, 60 ℃～200 ℃ reactions 0.5～72 hour, obtain head product; Component three consumptions are 5%～65% of steps A prepolymer total mass, and component four-function amount is 5%～48% of steps A prepolymer total mass.Step (C): step B is obtained head product, through precipitation, filtration, separation, drying, obtain containing the Hyperbranched Polyester Resin of polyhydroxy functional groups.
The Resins, epoxy that steps A of the present invention adopts or contain many epoxy group(ing) monomer and comprise one or more mixtures in common bisphenol A type epoxy resin (E-54, E-52, E-51, E-44, E-42, E-39, E-20, E-12, E-06, E-03), bisphenol f type epoxy resin, brominated bisphenol a type epoxy resin, the isocyanuric acid three-glycidyl ester.
The monomer that contains pure amine structure in the steps A of the present invention comprises the mixture of one or more monomers in thanomin, diethanolamine, diisopropanolamine (DIPA), the diglycolamine.
The monomer that contains cyclic acid anhydride that adopts among the step B of the present invention comprises that Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic anhydride, MALEIC ANHYDRIDE, alkyl replace a kind of monomer in MALEIC ANHYDRIDE, ring Pyroglutaric acid, cyclohexane diacid acid anhydride, the norbornene dicarboxylic anhydride or the mixture of several monomers.
The single epoxy group(ing) monomer that contains that adopts among the step B of the present invention comprises epoxy chloropropane, 1, a kind of monomer among 2-epoxy eicosane, butylglycidyl ether, phenyl glycidyl ether, glycidyl allyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether, lauryl diglycidyl ether, benzyl glycidyl ether, glycidyl acrylate, neodecanoic acid glycidyl ester, tertiary carbonic acid glycidyl ester, the KH-560 or the mixture of several monomers.
The non-protonic solvent that adopts among the present invention comprises the mixture of one or more solvents of methyl-sulphoxide, DMF, N,N-dimethylacetamide, tetrahydrofuran (THF), METHYLPYRROLIDONE, chloroform, tetracol phenixin.
The structure of the poly-hydroxy Hyperbranched Polyester Resin that the present invention synthesizes and molecular weight are confirmed through infrared spectra, nucleus magnetic resonance and gel permeation chromatography (GPC) analyses.When wherein GPC measures take DMF (DMF) as solvent.
Novel poly-hydroxy Hyperbranched Polyester Resin prepared in accordance with the present invention, raw material sources are extensive, low price, simple synthetic method, technique is simple, and controllability is good, and preparation cost is low, resulting polymers contains a large amount of hydroxy functional groups, solubility is good, and suitable biological medicine carrier, efficient coating, linking agent, water-absorbing material, special plastic and the additive thereof etc. done have a wide range of applications.
Embodiment
In reaction flask, at first add non-protonic solvent, then the component one (Resins, epoxy or contain the monomer of many epoxy group(ing)) and component two (monomer that contains pure amine structure) that add certain amount, temperature reaction behind the logical rare gas element is until the system oxirane value is lowered the temperature after being down to theoretical value; Add component three (monomer that contains cyclic acid anhydride) and the component four (monomer that contains single epoxy group(ing)) of certain amount in above-mentioned polymkeric substance, heating is reacted, and behind the reaction certain hour, obtains head product.Then with head product through precipitation, filtration, separation, drying, can obtain containing the Hyperbranched Polyester Resin of polyhydroxy functional groups.
Embodiment 1
In reaction flask, add 80gN; dinethylformamide and 100g Resins, epoxy E-12; then the diisopropanolamine (DIPA) that adds 17g is warming up under nitrogen protection and carries out ring-opening reaction about 110 ℃, is cooled to room temperature behind the reaction 4h; add 73g trimellitic anhydride and 63g epoxy chloropropane; be heated to 100 ℃ of insulation reaction to acid values and no longer change, obtain head product, then with head product through precipitation, filtration, separation, drying; obtain pulverulent solids, productive rate 83%.
Embodiment 2
In reaction flask, add 80gN; dinethylformamide and 50g isocyanuric acid three-glycidyl ester; then the diethanolamine that adds 53g is warming up under nitrogen protection and carries out ring-opening reaction about 110 ℃, is cooled to room temperature behind the reaction 4h; add 112g MALEIC ANHYDRIDE and 44g epoxy chloropropane; be heated to 100 ℃ of insulation reaction to acid values and no longer change, obtain head product, then with head product through precipitation, filtration, separation, drying; obtain pulverulent solids, productive rate 87%.
Embodiment 3
In reaction flask, add 100g METHYLPYRROLIDONE and 60g epoxy resin E-44; then the diisopropanolamine (DIPA) that adds 34g; under nitrogen protection, be warming up to and carry out ring-opening reaction about 110 ℃; be cooled to room temperature behind the reaction 4h, add 121g Tetra Hydro Phthalic Anhydride and 69g butylglycidyl ether, be heated to 120 ℃ of insulation reaction to acid values and no longer change; obtain head product; then with head product through precipitation, filtration, separation, drying, obtain pulverulent solids, productive rate 81%.
Embodiment 4
In reaction flask, add 200gN; N-N,N-DIMETHYLACETAMIDE and 50g Resins, epoxy E-12,80gE-51; then the diisopropanolamine (DIPA) that adds 62g; under nitrogen protection, be warming up to and carry out ring-opening reaction about 110 ℃; be cooled to room temperature behind the reaction 4h; add 96g trimellitic anhydride and 26g butylglycidyl ether and 81g phenyl glycidyl ether; being heated to 100 ℃ of insulation reaction to acid values no longer changes; obtain head product; then with head product through precipitation, filtration, separation, drying; obtain pulverulent solids, productive rate 80%.
Claims (9)
1. a preparation method who contains polyhydric Hyperbranched Polyester Resin is characterized in that the preparation method comprises the steps:
A. with component one: Resins, epoxy or contain monomer and the component two of many epoxy group(ing): the monomer that contains pure amine structure drops in the reaction flask, under protection of inert gas, under 60 ℃～260 ℃, in non-protonic solvent, react, reaction times is 0.5～35 hour, obtains containing the polymkeric substance of secondary hydroxyl; Described component one is 1: 0.7～3.5 with component two mol ratios;
B. the prepolymer that steps A is obtained is cooled to room temperature, adds component three: the monomer and the component four that contain cyclic acid anhydride: contain the monomer of single epoxy group(ing), under protection of inert gas, in 60 ℃～200 ℃ reactions 0.5～72 hour, obtain head product;
C. step B is obtained head product, through precipitation, filtration, separation, drying, obtain containing the Hyperbranched Polyester Resin of polyhydroxy functional groups.
2. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1, it is characterized in that, the consumption of component one is 28%～76.4%, component two consumptions are 16.1%～44.7%, component three consumptions are 5%～65% of steps A prepolymer total mass, and component four-function amount is 5%～48% of steps A prepolymer total mass.
3. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1, it is characterized in that component one in the steps A: Resins, epoxy or contain many epoxy group(ing) monomer and comprise one or more mixtures in common bisphenol A type epoxy resin, bisphenol f type epoxy resin, brominated bisphenol a type epoxy resin, the isocyanuric acid three-glycidyl ester.
4. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 3, it is characterized in that described common bisphenol A type epoxy resin comprises: one or more among E-54, E-52, E-51, E-44, E-42, E-39, E-20, E-12, E-06, the E-03.
5. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1, it is characterized in that component two in the steps A: the monomer that contains pure amine structure comprises the mixture of one or more monomers in thanomin, diethanolamine, diisopropanolamine (DIPA), the diglycolamine.
6. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1 is characterized in that component three among the step B: the monomer that contains cyclic acid anhydride comprises that Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic anhydride, MALEIC ANHYDRIDE, alkyl replace a kind of monomer in MALEIC ANHYDRIDE, ring Pyroglutaric acid, cyclohexane diacid acid anhydride, the norbornene dicarboxylic anhydride or the mixture of several monomers.
7. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1, it is characterized in that component four among the step B: contain single epoxy group(ing) monomer and comprise epoxy chloropropane, 1, a kind of monomer among 2-epoxy eicosane, butylglycidyl ether, phenyl glycidyl ether, glycidyl allyl ether, ethylene glycol diglycidylether, butanediol diglycidyl ether, lauryl diglycidyl ether, benzyl glycidyl ether, glycidyl acrylate, neodecanoic acid glycidyl ester, tertiary carbonic acid glycidyl ester, the KH-560 or the mixture of several monomers.
8. the preparation method who contains polyhydric Hyperbranched Polyester Resin as claimed in claim 1, it is characterized in that non-protonic solvent comprises methyl-sulphoxide, N, the mixture of one or more solvents in dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), METHYLPYRROLIDONE, chloroform, the tetracol phenixin.
9. one kind contains polyhydric Hyperbranched Polyester Resin, it is characterized in that the hyperbranched polymer that adopts described each preparation method of claim 1～8 to obtain.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019121356A1 (en) | 2017-12-21 | 2019-06-27 | Covestro Deutschland Ag | Polycarbonate composition |
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| CN104628995B (en) * | 2015-01-13 | 2017-02-08 | 廊坊立邦涂料有限公司 | Hyperbranched epoxy resin as well as preparation method and application thereof in coating |
| CN104927656B (en) * | 2015-07-14 | 2017-04-05 | 扬州市祥华新材料科技有限公司 | A kind of anodized aluminium containing dissaving polymer separates coating and preparation method thereof |
| CN104962152B (en) * | 2015-07-14 | 2017-04-19 | 扬州市祥华新材料科技有限公司 | Alumite chromatographic dye containing hyperbranched polymer and preparation method of alumite chromatographic dye |
| CN106046288B (en) * | 2016-04-01 | 2019-02-19 | 华南师范大学 | A kind of hydrophilic chain extender and the preparation method and application thereof |
| JP6947102B2 (en) * | 2018-03-29 | 2021-10-13 | Jnc株式会社 | Thermosetting composition |
| CN109796363B (en) * | 2018-12-06 | 2020-12-22 | 华南理工大学 | Polyhydroxy low-viscosity star-shaped hydroxyl resin with hybrid arms and preparation method and application thereof |
| CN111978506B (en) * | 2019-05-23 | 2022-08-09 | 珠海瑞杰包装制品有限公司 | Preparation method of aqueous hyperbranched polyurethane acrylate emulsion, UV (ultraviolet) curing coating and preparation method and application thereof |
| CN111622017B (en) * | 2020-05-08 | 2022-02-08 | 仙鹤股份有限公司 | Low-air-permeability CTP plate lining paper and preparation method thereof |
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| US5418301A (en) * | 1992-02-26 | 1995-05-23 | Perstorp Ab | Dendritic macromolecule and process for preparation thereof |
| CN1470545A (en) * | 2003-06-20 | 2004-01-28 | 四川大学 | Method for preparing high-branched polyester |
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| US5418301A (en) * | 1992-02-26 | 1995-05-23 | Perstorp Ab | Dendritic macromolecule and process for preparation thereof |
| CN1470545A (en) * | 2003-06-20 | 2004-01-28 | 四川大学 | Method for preparing high-branched polyester |
Non-Patent Citations (1)
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| 童身毅，王黎.超支化聚酯树脂在涂料中的应用.《涂料工业》.2007,第37卷(第1期),第39-42页. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121356A1 (en) | 2017-12-21 | 2019-06-27 | Covestro Deutschland Ag | Polycarbonate composition |
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