CN107189053B - Preparation method and application under a kind of polynary carbonic ester resin and its normal pressure - Google Patents

Preparation method and application under a kind of polynary carbonic ester resin and its normal pressure Download PDF

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CN107189053B
CN107189053B CN201710339537.4A CN201710339537A CN107189053B CN 107189053 B CN107189053 B CN 107189053B CN 201710339537 A CN201710339537 A CN 201710339537A CN 107189053 B CN107189053 B CN 107189053B
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carbonic ester
ester resin
polynary
resin
normal pressure
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CN107189053A (en
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瞿金清
王彩
陈荣华
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CARPOLY CHEMICAL GROUP Co Ltd
South China University of Technology SCUT
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CARPOLY CHEMICAL GROUP Co Ltd
South China University of Technology SCUT
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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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/323—General preparatory processes using carbon dioxide and alcohols
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Epoxy Resins (AREA)

Abstract

The invention discloses preparation methods under a kind of polynary carbonic ester resin and its normal pressure and application.This method is using acid anhydrides, polyalcohol, epoxychloropropane as Material synthesis epichlorohydrin resin, further with bicarbonate in catalyst and CO2Polynary carbonic ester resin is synthesized under atmosphere.The preparation of carbonic ester resin can react, technique and equipment are simple, and the reaction time is shorter, and raw material is easy to get without carrying out under conditions of high temperature and pressure under normal pressure in the present invention.The carbonic ester resin volatility of preparation is low, substantially nontoxic, and has good biological degradability.Larger raising has been obtained with the mechanical property of its non-isocyanate polyurethane synthesized with polyamine and resistant to chemical media, media-resistant permeability is greatly reduced, and synthesis process is not influenced by moisture, is expected to become a kind of green material of good performance instead of conventional urethane.

Description

Preparation method and application under a kind of polynary carbonic ester resin and its normal pressure
Technical field
The present invention relates to a kind of polynary carbonic ester resins, more particularly to a kind of polynary carbonic ester resin and its normal pressure Lower preparation method and application.
Background technique
Polyurethane is that one kind has again in fields such as plastics, rubber, foam, fiber, coating, adhesive and functional polymers The synthesis high molecular material of big application value, it has also become indispensable chemical materials in human lives.Conventional urethane material Usually formed by polyalcohol and isocyanate polymeric, and isocyanates is a kind of hypertoxicity substance that harm to the human body is very big, this Safe and environment-friendly developing direction is not met.And isocyanates can react with water to the moisture-sensitive in environment and generate titanium dioxide Carbon, bubble rests in film or surface forms defect, causes coating bubbles and closure to reduce, influences the resistant to chemical media of material Property and dicoration.In addition, containing multiple duplicate " carbamate " groups in polyurethane molecular chain, unstable chemical bond makes The hydrolytic resistance of material is poor, permeability resistance is insufficient, affects its application in terms of compound matrix material and heavy anticorrosive material.Closely Nian Lai, as increasingly prominent and petroleum resources scarcity, the environmentally protective, low-carbon high-efficiency increasingly of environmental problem have become polyurethane Industry the main direction of development.Various renewable bio-based polyurethanes, aqueous polyurethane etc. continue to bring out.But these are not all solved Certainly hypertoxicity substance isocyanates uses this critical problem.
Non-isocyanate polyurethane (abbreviation NIPU) is new as made of cyclic carbonate ester oligomer and primary amine oligomerization precursor reactant Generation environment-protecting polyurethane, not using isocyanates as raw material, production technology and product itself safety and environmental protection can thoroughly change poly- for it Urethane industry is high-risk, high poison, the status of high pollution.Compared with traditional PU material, β carbon atoms in NIPU carbamate segment On hydroxyl can form intramolecular hydrogen bond with its carbonyl, there is stronger molecular force, while abandon moisture-sensitive raw material isocyanide The use of acid esters, stores more convenient, and the hydrolytic resistance of material, chemical resistance and anti-permeability performance are more excellent.
Chinese patent CN102731779A is by epoxy resin and CO2A period of time generation is reacted under certain temperature and pressure End group contains the cyclic carbonate ester of epoxy group.Then this compound is mixed with primary amine, reacted by epoxy group with amino and Cyclocarbonate radical is reacted with amino generates hybrid non-isocyanate polyurethane.The synthetic method is environmentally friendly, simple, and synthetic product is simultaneously Good risk energy with epoxy resin and polyurethane, the physics such as caking property, acid-alkali-corrosive-resisting, solvent resistance, mechanical strength Performance is more excellent, and still, synthesis condition needs to complete under high pressure, higher to equipment requirement, reaction process safety by Large effect.
It, then can be efficiently against CO using chlorohydrination synthesizing cyclic carbonate ester2It is inserted into needed for this method of epoxy resin The shortcomings that condition of high voltage, reaction system only need certain CO2Atmosphere, and simple process, general reaction unit Reach requirement, the corresponding reaction time also greatly shortens.Meanwhile reaction temperature is relatively low, has further ensured reaction Safety carries out.The polynary carbonic ester resin resin of synthesis is substantially nontoxic, and biological degradability is good.
" synthesis and characterization of polynary carbonic ester resin resin, Wang Fang etc. bond magazine, 2008,29 (1): 6-9 " to paper It discloses using epoxy resin E-44 as raw material, so that epoxy group is converted into five-membered ring carbonate ester in the presence of high temperature, high pressure, catalyst Base, and by FT-IR,1The methods of H NMR, elemental analysis, GPC characterize cyclic carbonate ester；It is discussed in detail catalyst The influence to epoxy group conversion ratio and product appearance such as type, reaction temperature, reaction pressure, reaction time；The result shows that when Temperature is at 100 DEG C, and pressure carbon dioxide is in 1.5MPa, using four butyl bromation amine and potassium bromide as catalyst, reacts 5h, epoxy group Conversion ratio up to 95% or more, and product appearance is preferable.But the prior art needs to react at high temperature under high pressure, to setting Standby to require high, production cost rises, and the safety of operation is lower, and in product only the end of the chain there are two five-membered ring carbonate ester base, Since the reactivity of secondary amine and cyclocarbonate radical is far below primary amine, what the polynary amine curing with primary amine number less than 3 frequently resulted in It is linear polymeric, it is poor compared with the film performance of cross-linked structure.
Summary of the invention
In view of the problems of the existing technology the present invention, provides and synthesizes polynary carbonic ester resin synthesis under a kind of normal pressure New process, avoid the reaction condition of the harshness such as high temperature and pressure, shorten the reaction time, reduce equipment requirement, technique letter Single, raw material is easy to get.
Another object of the present invention is to provide a kind of mechanical performance and chemical resistance is more preferably polynary compared with traditional PU Carbonic ester resin；
Further object of the present invention is to provide application of the polynary carbonic ester resin in metal protective coating, this The non-isocyanate polyurethane that the polynary carbonic ester resin and polynary amine curing for inventing synthesis obtain, hardness, patience, attachment Power, mechanical property are all more preferable than traditional PU.
The object of the invention is achieved through the following technical solutions:
The method of polynary carbonic ester resin is prepared under a kind of normal pressure, comprising the following steps:
1) preparation of epichlorohydrin resin: acid anhydrides, polyalcohol and the first solvent are mixed, and are warming up to 90-120 DEG C, keep the temperature 3-5h, The first catalyst is added and epoxychloropropane is added dropwise, keeps the temperature 6-8h, after the acid value of resin is less than 15mgKOH/g, cooling discharge；
The polyalcohol is 2,4- diethyl -1,5-PD (PD-9), 1,4-butanediol (BDO), trihydroxy methyl third One or more of alkane (TMP), double trimethylolpropane (TMP), pentaerythrite (PE) and dipentaerythritol (PE) are mixed Close object；
The acid anhydrides is one or more mixtures of phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride；
The catalyst is tetraethylammonium bromide, tetrabutylammonium bromide, triphenylphosphine, tetramethyl ammonium chloride and benzyl three One or more mixtures of ethyl ammonium chloride；
2) preparation of polynary carbonic ester resin: the epichlorohydrin resin, carbonic acid class salt and the second solvent are mixed, and are added the Two catalyst, are passed through CO2After rise to 80-110 DEG C, keep the temperature 5-9h, obtain weak yellow liquid, cool down filtering and discharging；
The carbonic acid class salt is one or more mixtures of carbonate and bicarbonate；
Second catalyst is tetrabutylammonium bromide, 18- crown- 6, LiBr, KI and cetyl trimethylammonium bromide One or more mixtures of.
To further realize the object of the invention, it is preferable that in terms of quality percentage, prepare the raw material composition of epichlorohydrin resin are as follows: Acid anhydrides 38-45%, epoxychloropropane (ECH) 24-31%, polyalcohol 7-21%, the first catalyst 0.1-0.5%；Remaining is molten Agent.
Preferably, by percentage to the quality, it prepares raw material in polynary carbonic ester resin to form are as follows: epichlorohydrin resin 40- 55%, bicarbonate 28-40%, the second catalyst 0.5-1.5%；Remaining is the second solvent.
Preferably, first solvent is ethyl acetate, butyl acetate, toluene, dimethylformamide (DMF) and methyl One or more mixtures of isobutyl ketone.
Preferably, second solvent is dimethyl sulfoxide (DMSO), dimethylformamide (DMF), 1- methyl -2- pyrrole One or more mixtures of pyrrolidone (NMP) and acetonitrile.
Preferably, the bicarbonate includes NaHCO3Or KHCO3；The carbonate includes K2CO3Or Na2CO3。
Preferably, the epichlorohydrin resin is transparent viscous liquid, and acid value is less than 15mgKOH/g；Solid content 65-85%, Viscosity is 600-8600mPas.
A kind of polynary carbonic ester resin, is made by the above method, and the structural formula of the polynary carbonic ester resin is；Wherein n is the number of the group containing cyclic carbonate ester on molecular resin chain, n ≥2；The percentage composition 15-40% of cyclic carbonate ester group, the solid content 40-70% of polynary carbonic ester resin are sticked at 25 DEG C Degree is 20-600mPas.
Application of the polynary carbonic ester resin in metal protective coating.The coating contains polynary carbonic ester resin And polyamine curing agent；- the NH in cyclocarbonate radical and polyamine curing agent in the polynary carbonic ester resin2Rub You are than being 1:0.90-1.5；The polyamine curing agent is hexamethylene diamine, isophorone diamine, triethylene tetramine, polyetheramine, gathers One of aziridine and tetraethylenepentamine or a variety of mixtures.
Basic principle of the invention: occur half-esterification to react to obtain small point with multiple carboxyls using polyalcohol and acid anhydrides Sub- compound, then ring-opening reaction occurs under the effect of the catalyst for carboxyl and epoxychloropropane, generates multiple end neighbour chlorine hydroxyls Functional group under certain temperature, then reacts to obtain polynary ring carbon acid with bicarbonate under the action of quaternary ammonium salt phase transfer catalyst Ester resin.The polynary carbonic ester resin molecule volatility generated is small, substantially nontoxic, and biological degradability is excellent.The method is not It needs to react at high temperature under high pressure, therefore equipment and technology is simple, and the reaction time is not also grown.Wave number 1800cm in attached drawing 1-1Place It can be seen that the generation of cyclocarbonate radical.It is the hydrogen on methine on cyclocarbonate radical that the wave crest at 1 is marked in attached drawing 2 Peak.The non-isocyanate film adhesive for acting on synthesis with the cyclic carbonate ester of above-mentioned synthesis and polyamine is fabulous, water resistance with it is resistance to Chemicals etc. are all good compared with conventional urethane.
The preparation of polynary carbonic ester resin of the invention has the advantage that compared with prior art
(1) this method need to only carry out reacting under normal pressure, avoid the high temperature and pressure in conventional method, to setting Low for requiring, simple process, operational safety is improved, and the reaction time is shorter, and raw material is easy to get, and reduces manufacturing cost；
(2) process of synthesizing cyclic carbonate ester is in CO2It is carried out under atmosphere, consumes greenhouse gases, this route is environmentally protective；
(3) the polynary carbonic ester resin of this method preparation can have for nonisocyanate polyurethane synthesized to avoid a variety of The participation of noxious material, reaction process without carrying out in anhydrous conditions, and the water-fast chemical-resistant of film generated is more excellent.
Detailed description of the invention
Fig. 1 is the infrared spectrogram for the polynary carbonic ester resin that embodiment 1 obtains.
Fig. 2 is the polynary carbonic ester resin that embodiment 1 obtains1H NMR figure.
Specific embodiment
For a better understanding of the invention, present invention will be further explained below with reference to the attached drawings and examples, but the present invention Embodiment be not limited only to this.
Polynary carbonic ester resin resin prepared by the present invention and its non-isocyanate polyurethane of synthesis are with the following method It is characterized: polynary 2000 Fourier infrared spectrograph of carbonic ester resin resin structure Spectrum；German Bruker is public Take charge of 400 type Nuclear Magnetic Resonance Spectrometer nuclear magnetic resonance spectrometer of ADVNCE；CSPM-3000 The surface topography of atomic force microscope (AFM) observation film；Hardness of film is tested according to GB/T6739-1996.Using in Soxhlet (soxhlet) method for measuring dry coating quality afterwards for 24 hours is continuously extracted with tetrahydrofuran (THF) in extractor, be calculated The degree of cross linking；The test of film medium-resistance is to measure water absorption rate and suction ethyl alcohol rate and its mistake in water and ethyl alcohol of film Rate again.Viscosity is measured at 25 DEG C using Brookfield company LVT type rotational viscometer；Solid content GB/ according to national standards T1725-79 test.
Embodiment 1
(1) epichlorohydrin resin is prepared:
Formula:
Table 1a
Preparation method: the benzene of metering is added in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating paddle and constant pressure funnel Acid anhydride, polyalcohol pentaerythrite and solvent acetic acid butyl ester rise to 110 DEG C, keep the temperature 4h, add catalyst tetrabutylammonium bromide and start to drip Add epoxychloropropane, keep the temperature 6h, after the acid value of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance: colourless transparent liquid；Acid value: 10.78mgKOH/g；Solid content: 85.77%, viscosity: 8600mPa·s。
(2) polynary carbonic ester resin resin is prepared
Formula:
Table 1b
Preparation method: the chloropharin tree of the above-mentioned synthesis of metering is added in the four-hole boiling flask equipped with thermometer and agitating paddle Rouge, bicarbonate NaHCO3With solvent dimethyl sulfoxide, adds catalyst tetrabutylammonium bromide, be passed through CO2After rise to 80 DEG C, heat preservation 1h is again heated to 85 DEG C of heat preservation 1h, then rises to 90 DEG C of heat preservation 3h, finally in 100 DEG C of heat preservation 3h, obtains weak yellow liquid, cooling Filtering and discharging.
The NIPU obtained after the carbonic ester resin of synthesis and polynary amine curing is compareed with tradition PU performance and is shown in Table 1c:
Table 1c NIPU and PU film comprehensive performance
a- CC refers to cyclocarbonate radical
Fig. 1 is the infrared spectrogram of the tetra functional carbonic ester resin synthesized by pentaerythrite by two steps, infrared light 1730cm in spectrogram-1It is ester carbonyl stretching vibration absorption peak, and 1800cm-1Place is then the characteristic absorption peak of cyclocarbonate radical, table It is bright to successfully synthesize carbonic ester resin；The conversion ratio of cyclic carbonate ester can be obtained by nuclear-magnetism.Fig. 2 is passed through by pentaerythrite The tetra functional carbonic ester resin of two steps synthesis1H NMR figure, wherein marking is methine in cyclic carbonate ester group at 1 On hydrogen peak, be the peak of hydrogen on the methylene being connected on the complete epichlorohydrin resin of unreacted with chlorine at mark 2, after integral by S1/(S1+S2) conversion ratio of cyclic carbonate ester group can be calculated.
Product of the present invention can be clear that the generation of cyclocarbonate radical by infrared spectroscopy Fig. 1, it was demonstrated that success Ground has synthesized target product, it is seen that and the present invention synthesizes the feasibility of polynary carbonic ester resin resin under normal pressure, and Compared with the CO under high pressure2Insertion, reaction time foreshorten to 8h by tens hours, and reaction temperature is also lower, 100 DEG C with Interior, safety is improved, production cost decline.
The carbonic ester resin performance of the present embodiment synthesis: weak yellow liquid；Cyclocarbonate radical content 40%, solid contains Amount: 72.00%, viscosity: 600mPas；It further reacts to obtain non-isocyanate polyurethane with polyethyleneimine Film is water-fast, and alcohol resistance is good, and hardness reaches 2H, and flexibility can also be improved by 1mm thickness clamping plate, gloss；Known by table 1c, this The non-isocyanate polyurethane that the polynary carbonic ester resin and polynary amine curing for inventing synthesis obtain, hardness, patience, attachment Power, mechanical property are all more preferable than traditional PU.This is because five-membered ring carbonate ester base reacts the carbamate segment generated with amine In the position β carbon atom on hydroxyl and its carbonyl formed intramolecular hydrogen bond, keep non-isocyanate polyurethane chemical structure more steady Fixed, the mechanical performance and chemical resistance of material are more preferably compared with traditional PU.
Under the premise of the water-fast chemical-resistant of film of especially the present embodiment generation is more excellent, preparation method route is green Colour circle is protected, and avoids the toxic chemicals such as phosgene without the use of high toxic materials synthesizing isocyanate, synthesis processes such as phosgene It uses, no longer to water extreme sensitivity, the present embodiment need to only carry out reacting whole preparation process under normal pressure, avoid High temperature and pressure in conventional method, low for equipment requirements, technique is simpler, and operational safety is improved, with the prior art Synthetic method is compared, and has apparent environmental protection, safety, easy advantage；And the reaction time is shorter, raw material is easy to get, and reduces generation Cost；The process of synthesizing cyclic carbonate ester resin of the present invention is in CO2It is carried out under atmosphere, consumes greenhouse gases, this route green ring It protects.
Embodiment 2
(1) epichlorohydrin resin is prepared:
Formula:
Table 2a
Preparation method: the equal of metering is added in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating paddle and constant pressure funnel Benzene tetracarboxylic acid acid anhydride, dihydric alcohol 1,4-butanediol and solvent dimethylformamide rise to 90 DEG C, keep the temperature 5h, add catalyst tetraethyl Ammonium bromide simultaneously starts that epoxychloropropane is added dropwise, and keeps the temperature 7h, after the acid value of resin is less than 15mgKOH/g, except cooling down out after solvent Material.
Epichlorohydrin resin performance: orange-yellow transparency liquid；Acid value: 13.08mgKOH/g；Solid content: 76.88%, viscosity: 1596mPa·s；
(2) polynary carbonic ester resin resin is prepared
Formula:
Table 2b
Preparation method: the chloropharin tree of the above-mentioned synthesis of metering is added in the four-hole boiling flask equipped with thermometer and agitating paddle Rouge, bicarbonate NaHCO3And solvent dimethylformamide, add catalyst lithium bromide, is passed through CO2After rise to 90 DEG C, keep the temperature 5h, then 100 DEG C of heat preservation 4h are heated to, weak yellow liquid is obtained, cool down filtering and discharging.
Carbonic ester resin performance: weak yellow liquid；Cyclocarbonate radical content 15%, solid content: 68.81%, viscosity: 551mPa·s；Good with the water-fast alcohol resistance of film after ethylenediamine solidification, hardness is up to 2H, and stability, mechanical property are also compared with tradition PU is more preferably.
Embodiment 3
(1) epichlorohydrin resin is prepared:
Formula:
Table 3a
Preparation method: the inclined of metering is added in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating paddle and constant pressure funnel Benzenetricarboxylic anhydride, polyalcohol pentaerythrite and solvent dimethylformamide rise to 100 DEG C, keep the temperature 5h, add catalyst tetrabutyl phosphonium bromide Ammonium simultaneously starts that epoxychloropropane is added dropwise, and 8h is kept the temperature, after the acid value of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance: claret transparency liquid；Acid value: 11.58mgKOH/g；Solid content: 60.80%, viscosity: 622mPa·s；
(2) polynary carbonic ester resin resin is prepared
Formula:
Table 3b
Preparation method: the chloropharin tree of the above-mentioned synthesis of metering is added in the four-hole boiling flask equipped with thermometer and agitating paddle Rouge, bicarbonate Na2CO3And solvent dimethylformamide, add catalyst tetrabutylammonium bromide (TBAB), is passed through CO2After rise to 80 DEG C, 5h is kept the temperature, 90 DEG C of heat preservation 3h are again heated to, obtains weak yellow liquid, cool down filtering and discharging.
Carbonic ester resin performance: weak yellow liquid；Cyclocarbonate radical content 25%, solid content: 69.02%, viscosity: 580mPa·s；Good with the water-fast alcohol resistance of film after hexamethylene diamine solidification, hardness is up to 2H, and stability, mechanical property are also compared with tradition PU is more preferably.
Embodiment 4
(1) epichlorohydrin resin is prepared:
Formula:
Table 4a
Preparation method: the benzene of metering is added in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating paddle and constant pressure funnel Acid anhydride, trihydroxylic alcohol trimethylolpropane (TMP) and solvent ethyl acetate rise to 100 DEG C, keep the temperature 3h, add catalyst tetrabutyl phosphonium bromide Ammonium simultaneously starts that epoxychloropropane is added dropwise, and 6h is kept the temperature, after the acid value of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance: colourless transparent liquid；Acid value: 9.67mgKOH/g；Solid content: 64.26%, viscosity: 602mPa·s；
(2) polynary carbonic ester resin resin is prepared
Formula:
Table 4b
Preparation method: the chloropharin tree of the above-mentioned synthesis of metering is added in the four-hole boiling flask equipped with thermometer and agitating paddle Rouge, bicarbonate K2CO3And solvent acetonitrile, add catalyst KI and 18- crown- 6, is passed through CO2After rise to 90 DEG C, keep the temperature 8h, obtain light Yellow liquid, cool down filtering and discharging.
Carbonic ester resin performance: weak yellow liquid；Cyclocarbonate radical content 35%, solid content: 68.35%, viscosity: 156mPa·s；Good with the water-fast alcohol resistance of film after polyether diamine solidification, hardness is up to 3H, and stability, mechanical property are also compared with biography PU unite more preferably；
Embodiment 5
(1) epichlorohydrin resin is prepared:
Formula:
Table 5a
Preparation method: the benzene of metering is added in the four-hole boiling flask equipped with thermometer, condenser pipe, agitating paddle and constant pressure funnel Acid anhydride, dihydric alcohol PD-9 and solvent toluene rise to 110 DEG C, keep the temperature 3h, add catalyst tetrabutylammonium bromide (TBAB) and start to be added dropwise Epoxychloropropane keeps the temperature 6h, after the acid value of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance: colourless transparent liquid；Acid value: 8.99mgKOH/g；Solid content: 80.68%, viscosity: 890mPa·s；
(2) polynary carbonic ester resin resin is prepared
Formula:
Table 5b
Preparation method: the chloropharin tree of the above-mentioned synthesis of metering is added in the four-hole boiling flask equipped with thermometer and agitating paddle Rouge, bicarbonate KHCO3With solvent 1-Methyl-2-Pyrrolidone (NMP), adds catalyst cetyl ammonium bromide, be passed through CO2Afterwards 100 DEG C are risen to, 9h is kept the temperature, obtains weak yellow liquid, cool down filtering and discharging.
Carbonic ester resin performance: weak yellow liquid；Cyclocarbonate radical content 24%, solid content: 41.60%, viscosity: 20mPa·s；
Good with the water-fast alcohol resistance of film after diethylenetriamine solidification, hardness is up to 3H, and stability, mechanical property are also compared with biography PU unite more preferably.

Claims (10)

1. preparing the method for polynary carbonic ester resin under a kind of normal pressure, it is characterised in that the following steps are included:
1) preparation of epichlorohydrin resin: acid anhydrides, polyalcohol and the first solvent are mixed, and are warming up to 90-120 DEG C, keep the temperature 3-5h, are added Simultaneously epoxychloropropane is added dropwise in first catalyst, keeps the temperature 6-8h, after the acid value of resin is less than 15mgKOH/g, cooling discharge；
The polyalcohol is 2,4- diethyl -1,5-PD, 1,4-butanediol, trimethylolpropane, double trihydroxy methyls third One or more mixtures of alkane, pentaerythrite and dipentaerythritol；
The acid anhydrides is one or more mixtures of phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride；
The catalyst is tetraethylammonium bromide, tetrabutylammonium bromide, triphenylphosphine, tetramethyl ammonium chloride and benzyl triethyl ammonium One or more mixtures of ammonium chloride；
2) preparation of polynary carbonic ester resin: the epichlorohydrin resin, carbonic acid class salt and the second solvent are mixed, and are added second and are urged Agent is passed through CO2After rise to 80-110 DEG C, keep the temperature 5-9h, obtain weak yellow liquid, cool down filtering and discharging；
The carbonic acid class salt is one or more mixtures of carbonate and bicarbonate；
Second catalyst is tetrabutylammonium bromide, 18- crown- 6, in LiBr, KI and cetyl trimethylammonium bromide One or more kinds of mixtures.
2. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: with quality hundred Point meter, prepares the raw material composition of epichlorohydrin resin are as follows: acid anhydrides 38-45%, epoxychloropropane 24-31%, polyalcohol 7-21%, and first Catalyst 0.1-0.5%；Remaining is solvent.
3. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: with quality hundred Divide than meter, prepares raw material in polynary carbonic ester resin and form are as follows: epichlorohydrin resin 40-55%, bicarbonate 28-40%, second Catalyst 0.5-1.5%；Remaining is the second solvent.
4. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: described One solvent is that one or more of ethyl acetate, butyl acetate, toluene, dimethylformamide and methyl iso-butyl ketone (MIBK) are mixed Close object.
5. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: described Two solvents are the mixing of one or more of dimethyl sulfoxide, dimethylformamide, 1-Methyl-2-Pyrrolidone and acetonitrile Object.
6. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: the carbonic acid Hydrogen salt includes NaHCO3Or KHCO3；The carbonate includes K2CO3Or Na2CO3。
7. preparing the method for polynary carbonic ester resin under normal pressure according to claim 1, it is characterised in that: the chloropharin Resin is transparent viscous liquid, and acid value is less than 15mgKOH/g；Solid content 65-85%, viscosity 600-8600mPas.
8. a kind of polynary carbonic ester resin, it is characterised in that: it is made by any one of claim 1-7 the method, this is more The structural formula of membered ring carbonate resin is；Wherein n is molecular resin The number of the group containing cyclic carbonate ester, n >=2 on chain；The percentage composition 15-40% of cyclic carbonate ester group, polynary carbonic ester resin Solid content 40-70%, viscosity is 20-600mPas at 25 DEG C；R is 2,4- diethyl -1,5-PD, Isosorbide-5-Nitrae-fourth two Remaining group after alcohol, trimethylolpropane, double trimethylolpropane, pentaerythrite or dipentaerythritol reaction.
9. application of the polynary carbonic ester resin in metal protective coating described in claim 8.
10. application of the polynary carbonic ester resin according to claim 9 in metal protective coating, it is characterised in that: The coating contains polynary carbonic ester resin and polyamine curing agent；Cyclocarbonate radical in the polynary carbonic ester resin With-the NH in polyamine curing agent2Molar ratio be 1:0.90-1.5；The polyamine curing agent is hexamethylene diamine, different Fo Er One of ketone diamines, triethylene tetramine, polyetheramine, polyethyleneimine and tetraethylenepentamine or a variety of mixtures.
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