CN106188567A - A kind of synthetic technology of Aromatic Hyperbranched Polyesters type epoxy resin - Google Patents

A kind of synthetic technology of Aromatic Hyperbranched Polyesters type epoxy resin Download PDF

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Publication number
CN106188567A
CN106188567A CN201610766624.3A CN201610766624A CN106188567A CN 106188567 A CN106188567 A CN 106188567A CN 201610766624 A CN201610766624 A CN 201610766624A CN 106188567 A CN106188567 A CN 106188567A
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China
Prior art keywords
aromatic
type epoxy
reaction
epoxy resin
hyperbranched polyesters
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Pending
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CN201610766624.3A
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Chinese (zh)
Inventor
刘燕军
邵建楠
杨俊玲
郑帼
周存
徐进云
孙玉
吴波
贾辉
刘鹏雷
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Priority to CN201610766624.3A priority Critical patent/CN106188567A/en
Publication of CN106188567A publication Critical patent/CN106188567A/en
Pending legal-status Critical Current

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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
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C08G83/006—After treatment of hyperbranched macromolecules

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention intends the aromatic polycarboxylic acid for different structure and generates the Aromatic Hyperbranched Polyesters type epoxy resin of different branched structures from polyol reaction.This method is so that aromatic polyvalent is sour and polyhydric alcohol is as raw material, add solvent to react, obtain the end carboxyl super branched polyester of intermediate product, add catalyst and epoxy halogenated hydrocarbons, obtain superbrnaching end-hydroxy polyester, add alkaline solution, be filtered to remove precipitation, reaction deviates from solvent after terminating, and obtains end product Aromatic Hyperbranched Polyesters type epoxy resin.Reaction end is determined by measuring the epoxide number of product.The preparation method technique of the present invention is simple, with low cost, and in the Aromatic Hyperbranched Polyesters type epoxy molecule of synthesis, nothing is wound around, viscosity is low, reactivity is high, the compatibility is good.

Description

A kind of synthetic technology of Aromatic Hyperbranched Polyesters type epoxy resin
Technical field
The present invention relates to the synthetic technology of a kind of Aromatic Hyperbranched Polyesters type epoxy resin.It is primarily adapted for use in synthesizing epoxy Resin.
Background technology
The developing history of dissaving polymer can trace back to for 19 end of the centurys, and Berzelius is first with tartaric acid (A2B2Single Body) and glycerol (B3Monomer) synthesize the resin with branched structure, pull open the prelude of dissaving polymer research from this. 1901, Watson reported phthalic anhydride (A2Monomer) and glycerol (B3Monomer) reaction of synthetic resin, through further Further investigation, the viscosity of the ratio of viscosities linear polymer of the polymer obtained by discovery phthalic anhydride and glycerine reaction Low.Since this kind of novel resin is synthesized, in place of people attempt to find its application.Baekeland in 1909 Report first commercialization plastics one phenolic resin, obtain soluble phenolics aldehydes prepolymer by formaldehyde and phenol reactant, so After again prepare crosslinking phenolic resin.Until the eighties in 20th century, dissaving polymer has just obtained real development.1982 Year, Kricheldorf passes through AB and AB2Monomer has been condensed to yield hyper-branched polyester.Within 1988, Kim and Webster uses a step Method has synthesized Hyperbranched polyphenylene, and this polymer is polydispersity, existing defects in highly branched in forming process Dendriform molecule, they are by its named dissaving polymer (HBP:Hyperbranched Polymer), up to the present people All use this title.Hyper-branched polyester is that a class is different from tradition linear polyesters, has highly-branched structure, esterification repetition Unit contains the new polymers of ester group.It is dissaving polymer evolution synthesizes relatively early, synthesis technique is more ripe, A kind of typical case's dissaving polymer that application is strong.
The synthetic method of the dissaving polymer that the present invention relates to is fairly simple, can use one-step synthesis method, simultaneously gained Polyester is made without purification or only need to carry out simple purification, the technique that enormously simplify extensive synthesis of super branched polymer Process, reduces cost, makes the industrialization of this kind polyester be possibly realized.
Summary of the invention
It is an object of the present invention to provide a kind of simple, with low cost, the Aromatic Hyperbranched Polyesters type epoxy resin of synthesis divides Without the synthetic method being wound around, viscosity is low, reactivity is high, the compatibility is good in son.
This method, so that aromatic polyvalent is sour and polyhydric alcohol is as raw material, adds solvent and reacts, obtain intermediate product end carboxylic Base hyper-branched polyester, adds catalyst and epoxy halogenated hydrocarbons, obtains superbrnaching end-hydroxy polyester, add alkaline solution, filters Removing precipitation, reaction deviates from solvent after terminating, and obtains end product epoxy resin.Determine by measuring the epoxide number of product Reaction end.
As a example by trimethylolpropane with trimellitic anhydride, reaction mechanism is as follows:
The first step:
Second step:
3rd step:
Heretofore described aromatic polyvalent acid is phthalic acid, M-phthalic acid, p-phthalic acid, trimellitic acid Acid anhydride etc.；Polyhydric alcohol is ethylene glycol, Polyethylene Glycol, glycerol, trihydroxy and propane, tetramethylolmethane, glucose etc.；Organic solvent is Any one or two or more mixture in acetylacetone,2,4-pentanedione, hexamethylene, benzene,toluene,xylene, DMF； Catalyst is tertiary amine, quaternary ammonium salt and metal-organic complex, as chromium acetylacetonate, tetrabutyl ammonium bromide, tetraethylammonium bromide and Triethylamine etc.；Epoxy halogenated hydrocarbons is epoxychloropropane, epoxy bromopropane etc.；Alkaline solution is NaOH, KOH, Na2CO3、K2CO3Water Solution etc..
In the present invention, the polyhydric alcohol of the first step and aromatic polyvalent acid consumption mol ratio are 1: 1-5；Reaction feed temperature is 60-100℃；Heating rate is 0.5-2 DEG C/min；Reaction temperature is 70 DEG C-150 DEG C；Response time is 2-5 hour；Organic molten Agent is 2-7: 1 with the mass ratio of aromatic polyvalent acid in reactant；In second step, epoxy halogenated hydrocarbons rubs with aromatic polycarboxylic acid consumption That ratio is for 1-1: 3, and catalyst amount is the 0.1%-0.5% of reactant gross mass, reaction temperature 70 DEG C-150 DEG C, the response time For 3-6 hour, in the 3rd step, alkali and epoxy halogenated hydrocarbons consumption mol ratio were 1: 1-2, were joined by alkali and used for alkaline aqueous solution, cooling Speed is 0.5-2 DEG C/min, reaction temperature 50 DEG C-90 DEG C, and the response time is 2-6 hour.
The present invention is after the completion of reaction at the condition abjection organic solvent that vacuum is-0.8～-0.9, and solvent can repeatedly follow Ring uses, and can cost-effective be avoided that again environment.
The present invention after the completion of reaction, uses hydrochloric acid acetone method to measure the epoxide number of product, calculates the conversion of reaction with this Rate.
Detailed description of the invention
The specific embodiment of the present invention is described below, but the present invention should not be limited by the examples.
Embodiment 1. trimethylolpropane and trimellitic anhydride reaction synthesis process
Weigh in the four-hole boiling flask that 17.29g trimellitic anhydride is equipped with condenser, thermometer, be subsequently adding 100mLN, Dinethylformamide, is passed through nitrogen, adds 4.02g trimethylolpropane, opens stirring and is slowly heated to 90 DEG C, reacts 2h After, add 0.5g tetraethylammonium bromide and 16.7mL epoxychloropropane, after reaction 3h, add 24.9g potassium carbonate, react 3h After, carry out decompression distillation removing DMF.Then, stopped reaction, start cooling.Take its epoxide number of sample test Determine its conversion ratio.The epoxide number of product is 0.181mmol/g, and product yield is 94.57%.
Embodiment 2. glycerol and trimellitic anhydride reaction synthesis process
Weigh in the four-hole boiling flask that 17.29g trimellitic anhydride is equipped with condenser, thermometer, be subsequently adding 100mLN, Dinethylformamide, is passed through nitrogen, adds 2.76g glycerol, opens stirring and is slowly heated to 90 DEG C, after reaction 2h, then Add 0.5g tetraethylammonium bromide and 16.7mL epoxychloropropane, after reaction 3h, add 24.9g potassium carbonate, after reaction 3h, enter Row decompression distillation removing DMF.Then, stopped reaction, start cooling.Take its epoxide number of sample test to determine Its conversion ratio.The epoxide number of product is 0.182mmol/g, and product yield is 95.09%.

Claims (10)

1. a synthetic technology for Aromatic Hyperbranched Polyesters type epoxy resin, its principle is as follows:
The first step:
Second step:
3rd step:
2., described in right 1, aromatic polyvalent acid is phthalic acid, M-phthalic acid, p-phthalic acid, trimellitic anhydride Deng；Polyhydric alcohol is ethylene glycol, Polyethylene Glycol, glycerol, trihydroxy and propane, tetramethylolmethane, glucose etc..
3., described in right 1, organic solvent is in acetylacetone,2,4-pentanedione, hexamethylene, benzene,toluene,xylene, DMF Any one or two or more mixture.
4., described in right 1, catalyst is tertiary amine, quaternary ammonium salt and metal-organic complex, such as chromium acetylacetonate, tetrabutyl phosphonium bromide Ammonium, tetraethylammonium bromide and triethylamine etc..
5., described in right 1, epoxy halogenated hydrocarbons is epoxychloropropane, epoxy bromopropane etc..
6., described in right 1, alkaline solution is NaOH, KOH, Na2CO3、K2CO3Aqueous solution etc..
7. described in right 1, in the first step, polyhydric alcohol and aromatic polyvalent acid consumption mol ratio are 1: 1-5, and organic solvent is with anti- Answering the mass ratio of aromatic polyvalent acid in thing is 2-7: 1, determines proportioning according to reactant difference；In second step epoxy halogenated hydrocarbons with Aromatic polycarboxylic acid consumption mol ratio is 1-1: 3；In 3rd step, alkali and epoxy halogenated hydrocarbons consumption mol ratio are 1: 1-2.
8., described in right 1, the first step is reacted feed temperature and is 60-100 DEG C；Heating rate is 0.5-2 DEG C/min；Reaction temperature Degree is 70 DEG C-150 DEG C；Reaction temperature 70-150 DEG C in second step；Initial reaction temperature 70 DEG C-150 DEG C in 3rd step, cooling speed Rate is 0.5-2 DEG C/min, reaction temperature 50 DEG C-90 DEG C.
9., described in right 1, in the first step, the response time is 2-5 hour；In second step, the response time is 3-6 hour；3rd step The middle response time is 2-6 hour.
10., described in right 1, in second step, catalyst amount is the 0.1%-0.5% of reactant gross mass.
CN201610766624.3A 2016-08-29 2016-08-29 A kind of synthetic technology of Aromatic Hyperbranched Polyesters type epoxy resin Pending CN106188567A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109316981A (en) * 2018-12-10 2019-02-12 天津工业大学 A kind of preparation method of the super hydrophilic polymer film with demulsification function
CN110760071A (en) * 2019-10-12 2020-02-07 青岛大学 Preparation method of novel dendritic high-viscosity oil viscosity reducer
CN111978506A (en) * 2019-05-23 2020-11-24 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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109316981A (en) * 2018-12-10 2019-02-12 天津工业大学 A kind of preparation method of the super hydrophilic polymer film with demulsification function
CN109316981B (en) * 2018-12-10 2021-03-09 天津工业大学 Preparation method of super-hydrophilic polymer membrane with demulsification function
CN111978506A (en) * 2019-05-23 2020-11-24 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
CN110760071A (en) * 2019-10-12 2020-02-07 青岛大学 Preparation method of novel dendritic high-viscosity oil viscosity reducer

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Application publication date: 20161207