CN107189053A - 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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CN107189053A
CN107189053A CN201710339537.4A CN201710339537A CN107189053A CN 107189053 A CN107189053 A CN 107189053A CN 201710339537 A CN201710339537 A CN 201710339537A CN 107189053 A CN107189053 A CN 107189053A
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carbonic ester
ester resin
resin
polynary
normal pressure
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CN107189053B (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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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20General preparatory processes
    • C08G64/32General preparatory processes using carbon dioxide
    • C08G64/323General preparatory processes using carbon dioxide and alcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04Aromatic polycarbonates
    • C08G64/06Aromatic polycarbonates not containing aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G71/00Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • 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 method 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 without being carried out under conditions of HTHP under normal pressure in the present invention, and technique and equipment are simple, and the reaction time is shorter, and raw material is easy to get.The carbonic ester resin volatility of preparation is low, substantially nontoxic, and with good biological degradability.Larger raising has been obtained with the mechanical property and resistant to chemical media of its non-isocyanate polyurethane synthesized with polyamine, media-resistant permeability is greatly reduced, and building-up process is not influenceed by moisture, it is expected to turn into a kind of green material of good performance of replacement 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 resin, more particularly to a kind of polynary carbonic ester resin and its normal pressure Lower preparation method and application.
Background technology
Polyurethane is that a class has weight in fields such as plastics, rubber, foam, fiber, coating, adhesive and functional polymers The synthesis high polymer material of big application value, it has also become indispensable chemical materials in human lives.Conventional urethane material Generally formed by polyalcohol and isocyanate polymeric, and isocyanates is a kind of harm to the human body very big hypertoxicity material, this Safe and environment-friendly developing direction is not met., can be with water reaction generation titanium dioxide and isocyanates is to the moisture-sensitive in environment Carbon, bubble is rested in film or surface forms defect, is caused coating bubbles and closure to reduce, is influenceed the resistant to chemical media of material Property and dicoration.In addition, containing " carbamate " group of multiple repetitions in polyurethane molecular chain, unstable chemical bond makes The hydrolytic resistance of material is poor, permeability resistance is not enough, have impact on its application in terms of compound matrix material and heavy anticorrosive material.Closely Nian Lai, with environmental problem increasingly highlight and petroleum resources it is increasingly deficient, environmental protection, low-carbon high-efficiency turn into polyurethane Industry main development direction.Various renewable bio-based polyurethanes, aqueous polyurethane etc. are continued to bring out.But these are not all solved Certainly this critical problem of the use of hypertoxicity material isocyanates.
Non-isocyanate polyurethane (abbreviation NIPU) is by the new of cyclic carbonate ester oligomer and primary amine oligomerization precursor reactant Generation environment-protecting polyurethane, it is not using isocyanates as raw material, and production technology and product safety and environmental protection itself can thoroughly change poly- Urethane industry is high-risk, high poison, the present situation of high pollution.Compared with traditional PU materials, β carbon atoms in NIPU carbamate segments On hydroxyl can with its carbonyl formation intramolecular hydrogen bond, with stronger molecular force, while abandoning moisture-sensitive raw material isocyanide The use of acid esters, stores more convenient, the hydrolytic resistance of material, chemical resistance and anti-permeability performance are more excellent.
Chinese patent CN102731779A is by epoxy resin and CO2Reaction a period of time generates under certain temperature and pressure End group contains the cyclic carbonate ester of epoxy radicals.Then this compound is mixed with primary amine, reacted by epoxy radicals and amino and Cyclocarbonate radical and amino reaction generation 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 its caking property, acid-alkali-corrosive-resisting, solvent resistance, mechanical strength Performance is more excellent, still, and synthesis condition needs to complete under high pressure, higher to equipment requirement, course of reaction security by Large effect.
, then can be efficiently against CO using chlorohydrination synthesizing cyclic carbonate ester2Needed for this method of insertion epoxy resin The shortcoming of condition of high voltage, reaction system only needs to certain CO2Atmosphere, and technique is simple, general reaction unit just can be with Requirement is reached, the corresponding reaction time also greatly shortens.Meanwhile, reaction temperature is relatively low, has further ensured reaction Safety is carried out.The polynary carbonic ester resin resin of synthesis is substantially nontoxic, and biological degradability is good.
Paper " synthesis of polynary carbonic ester resin resin and sign, Wang Fang etc., bond magazine, 2008,29 (1):6-9” Disclose using epoxy resin E-44 as raw material, epoxy radicals is converted into five-membered ring carbonate ester in the presence of high temperature, high pressure, catalyst Base, and by FT-IR,1The methods such as H NMR, elementary analysis, GPC are characterized to cyclic carbonate ester;It is discussed in detail catalyst The influence to epoxy radicals conversion ratio and product appearance such as species, reaction temperature, reaction pressure, reaction time;As a result show, when Temperature is at 100 DEG C, and pressure carbon dioxide is in 1.5MPa, using four butyl bromation amine and KBr as catalyst, reacts 5h, epoxy radicals Conversion ratio up to more than 95%, and product appearance is preferable.But the prior art needs to react at high temperature under high pressure, pair set Standby to require high, production cost rises, and the security of operation is lower, and only the end of the chain has two five-membered ring carbonate ester bases in product, Because the reactivity of secondary amine and cyclocarbonate radical is far below primary amine, what the polyamine solidification for being less than 3 with primary amine number was frequently resulted in It is linear polymeric, the film performance than cross-linked structure is poor.
The content of the invention
There is provided polynary carbonic ester resin synthesis is synthesized under a kind of normal pressure for the problem of present invention exists for prior art New technology, it is to avoid the harsh reaction condition such as HTHP, 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 more preferably polynary than traditional PU Carbonic ester resin;
Further object of the present invention is application of the offer polynary carbonic ester resin in metal protective coating, this The polynary carbonic ester resin and polyamine for inventing synthesis solidify obtained non-isocyanate polyurethane, its 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:
A kind of method that polynary carbonic ester resin is prepared under normal pressure, comprises the following steps:
1) preparation of epichlorohydrin resin:Acid anhydrides, polyalcohol and the first solvent are mixed, 90-120 DEG C is warming up to, 3-5h is incubated, Add the first catalyst and epoxychloropropane is added dropwise, be incubated 6-8h, after the acid number of resin is less than 15mgKOH/g, cooling discharge;
Described polyalcohol is 2,4- diethyl -1,5-PD (PD-9), BDO (BDO), trihydroxy methyl third It is more than one or both of alkane (TMP), double trimethylolpropane (TMP), pentaerythrite (PE) and bipentaerythrite (PE) mixed Compound;
Described acid anhydrides is one or both of phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride thing mixed above;
Described catalyst is tetraethylammonium bromide, TBAB, triphenylphosphine, tetramethyl ammonium chloride and benzyl three One or both of ethyl ammonium chloride thing mixed above;
2) preparation of polynary carbonic ester resin:The epichlorohydrin resin, carbonic acid class salt and the second solvent are mixed, the is added Two catalyst, are passed through CO2After rise to 80-110 DEG C, permanent alternating temperature is incubated 5-9h, obtains weak yellow liquid, and cool filtering and discharging;
Described carbonic acid class salt is one or both of carbonate and bicarbonate thing mixed above;
The second described catalyst is TBAB, 18- crown-s 6, LiBr, KI and cetyl trimethylammonium bromide One or both of thing mixed above.
Further to realize the object of the invention, it is preferable that in terms of quality percentage, the raw material composition for preparing epichlorohydrin resin is: 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, preparing raw material composition in polynary carbonic ester resin is:Epichlorohydrin resin 40- 55%th, bicarbonate 28-40%, the second catalyst 0.5-1.5%;Remaining is the second solvent.
Preferably, the first described solvent is ethyl acetate, butyl acetate, toluene, dimethylformamide (DMF) and methyl One or both of isobutyl ketone thing mixed above.
Preferably, the second described solvent is dimethyl sulfoxide (DMSO) (DMSO), dimethylformamide (DMF), 1- methyl -2- pyrroles One or both of pyrrolidone (NMP) and acetonitrile thing mixed above.
Preferably, the bicarbonate includes NaHCO3Or KHCO3;The carbonate includes K2CO3Or Na2CO3
Preferably, the epichlorohydrin resin is transparent viscous liquid, and acid number is less than 15KOH/g;Solids content 65-85%, is sticked Spend for 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 solids content 40-70% of polynary carbonic ester resin, are sticked at 25 DEG C Spend for 20-600mPas.
Application of the polynary carbonic ester resin in metal protective coating.The coating contains polynary carbonic ester resin And polyamine curing agent;Described polynary carbonic ester resin and polyamine curing agent mol ratio cyclic carbonate ester:NH2=1:0.90‐ 1.5;Described polyamine curing agent is hexamethylene diamine, IPD, triethylene tetramine, polyetheramine, polyethyleneimine and four One or more mixtures in the amine of ethene five.
The general principle of the present invention:Occur small point that half-esterification reaction obtains carrying multiple carboxyls using polyalcohol and acid anhydrides Sub- compound, then ring-opening reaction, the adjacent chlorine hydroxyls in the multiple ends of generation occur in the presence of catalyst for carboxyl and epoxychloropropane Under functional group, certain temperature, then in the presence of quaternary ammonium salt phase transfer catalyst with bicarbonate reaction obtain polynary ring carbon acid Ester resin.The polynary carbonic ester resin molecule volatility of generation is small, substantially nontoxic, and biological degradability is excellent.The method is not Need to react at high temperature under high pressure, therefore equipment and technology is simple, and the reaction time is not also long.Wave number 1800cm in accompanying drawing 1-1Place It can be seen that the generation of cyclocarbonate radical.It is the hydrogen on the methine on cyclocarbonate radical that the crest at 1 is marked in accompanying 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 than conventional urethane.
The preparation of the polynary carbonic ester resin of the present invention has advantages below compared with prior art:
(1) this method need to only carry out reacting at ambient pressure, it is to avoid the HTHP in conventional method, pair set Standby to require low, technique is simple, and processing 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 CO2Carried out under atmosphere, consume greenhouse gases, this route environmental protection;
(3) polynary carbonic ester resin prepared by this method is used to nonisocyanate polyurethane synthesized to avoid a variety of having The participation of noxious material, course of reaction without carrying out in anhydrous conditions, and the water-fast chemical-resistant of film of generation is more excellent.
Brief description of the drawings
Fig. 1 is the infrared spectrogram for the polynary carbonic ester resin that embodiment 1 is obtained.
Fig. 2 is the polynary carbonic ester resin that embodiment 1 is obtained1H NMR scheme.
Embodiment
To more fully understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but the present invention Embodiment be not limited only to this.
Polynary carbonic ester resin resin and its non-isocyanate polyurethane of synthesis prepared by the present invention is with the following method Characterized:The polynary carbonic ester resin resin structure Fourier infrared spectrographs of Spectrum 2000;German Bruker is public Take charge of the type Nuclear Magnetic Resonance Spectrometer nuclear magnetic resonance spectrometers of ADVNCE 400;CSPM-3000 AFM (AFM) observes the surface topography of film;Hardness of film is tested according to GB/T6739-1996.Using in Soxhlet (soxhlet) method that dry coating quality is measured after 24h is continuously extracted in extractor with tetrahydrofuran (THF), calculating is obtained The degree of cross linking;The test of film medium-resistance is to determine the water absorption rate of film and inhale ethanol rate and its mistake in water and ethanol Rate again.Viscosity is determined using Brookfield companies LVT types rotation viscometer at 25 DEG C;Solid content according to standard GB/T/ T1725-79 is tested.
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, are incubated 4h, plus catalyst TBAB and start drop Plus epoxychloropropane, 6h is incubated, after the acid number of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance:Colourless transparent liquid;Acid number:10.78mgKOH/g;Solids 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 Fat, bicarbonate NaHCO3With solvent dimethyl sulfoxide (DMSO), plus catalyst TBAB, CO is passed through2After rise to 80 DEG C, insulation 1h, is again heated to 85 DEG C of insulation 1h, then rises to 90 DEG C of insulation 3h, is finally incubated 3h at 100 DEG C, obtains weak yellow liquid, cools Filtering and discharging.
The NIPU that the carbonic ester resin of synthesis is obtained after solidifying with polyamine is compareed with tradition PU performances is shown in Table 1c:
Table 1c NIPU and PU film combination properties
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 absworption 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 scheme, wherein it is methine in cyclic carbonate ester group to mark at 1 On hydrogen peak, be at mark 2 after the peak of hydrogen on the methylene being connected on the complete epichlorohydrin resin of unreacted with chlorine, integration by S1/(S1+S2) conversion ratio for obtaining cyclocarbonate radical group can be calculated.
Product of the present invention can be clear that the generation of cyclocarbonate radical by infrared spectrum Fig. 1, it was demonstrated that success Ground has synthesized target product, it is seen that the present invention synthesizes the feasibility of polynary carbonic ester resin resin at ambient pressure, and Than the CO under high pressure2Insertion, the reaction time foreshortens to 8h by tens hours, and reaction temperature is also lower, 100 DEG C with Interior, security is improved, and production cost declines.
The carbonic ester resin performance of the present embodiment synthesis:Weak yellow liquid;Cyclocarbonate radical content 40%, solid contains Amount:72.00%, viscosity:600mPa·s;It further reacts with polyethyleneimine and obtains non-isocyanate polyurethane Film is water-fast, and alcohol resistance is good, and hardness reaches 2H, and pliability can also be improved by the thick clamping plates of 1mm, gloss;Known by table 1c, this The polynary carbonic ester resin and polyamine for inventing synthesis solidify obtained non-isocyanate polyurethane, its hardness, patience, attachment Power, mechanical property are all more preferable than traditional PU.This is due to the carbamate segment that five-membered ring carbonate ester base reacts generation with amine In β positions carbon atom on hydroxyl and its carbonyl formation intramolecular hydrogen bond, make non-isocyanate polyurethane chemical constitution more steady Fixed, the mechanical performance and chemical resistance of material are than traditional PU more preferably.
On the premise of the water-fast chemical-resistant of film of particularly the present embodiment generation is more excellent, preparation method route is green Colour circle is protected, and without the use of the high toxic material synthesizing isocyanate such as phosgene, building-up process avoids the toxic chemicals such as phosgene Use, whole preparation process is no longer to water extreme sensitivity, and the present embodiment need to only carry out reacting at ambient pressure, it is to avoid HTHP in conventional method, low for equipment requirements, technique is simpler, and processing safety is improved, with prior art Synthetic method is compared, and has obvious 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 CO2Carried out under atmosphere, consume greenhouse gases, this route green ring Protect.
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 BDO and solvent dimethylformamide, rise to 90 DEG C, are incubated 5h, plus catalyst tetraethyl Ammonium bromide simultaneously starts that epoxychloropropane is added dropwise, and is incubated 7h, after the acid number of resin is less than 15mgKOH/g, except cooling after solvent Material.
Epichlorohydrin resin performance:Orange-yellow transparency liquid;Acid number:13.08mgKOH/g;Solids 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 Fat, bicarbonate NaHCO3And solvent dimethylformamide, plus catalyst lithium bromide, it is passed through CO2After rise to 90 DEG C, be incubated 5h, then 100 DEG C of insulation 4h are heated to, weak yellow liquid is obtained, cool filtering and discharging.
Carbonic ester resin performance:Weak yellow liquid;Cyclocarbonate radical content 15%, solids 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 than 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, are incubated 5h, plus catalyst tetrabutyl phosphonium bromide Ammonium simultaneously starts that epoxychloropropane is added dropwise, and 8h is incubated, after the acid number of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance:Claret transparency liquid;Acid number:11.58mgKOH/g;Solids 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 Fat, bicarbonate Na2CO3And solvent dimethylformamide, plus catalyst TBAB (TBAB), it is passed through CO2After rise to 80 DEG C, 5h is incubated, 90 DEG C of insulation 3h is again heated to, obtains weak yellow liquid, cool filtering and discharging.
Carbonic ester resin performance:Weak yellow liquid;Cyclocarbonate radical content 25%, solids 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 than 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, are incubated 3h, plus catalyst tetrabutyl phosphonium bromide Ammonium simultaneously starts that epoxychloropropane is added dropwise, and 6h is incubated, after the acid number of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance:Colourless transparent liquid;Acid number:9.67mgKOH/g;Solids 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 Fat, bicarbonate K2CO3And solvent acetonitrile, plus catalyst KI and 18- crown- 6, it is passed through CO2After rise to 90 DEG C, be incubated 8h, obtain light Yellow liquid, cool filtering and discharging.
Carbonic ester resin performance:Weak yellow liquid;Cyclocarbonate radical content 35%, solids 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 than 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, are incubated 3h, plus catalyst TBAB (TBAB) and start to be added dropwise Epoxychloropropane, is incubated 6h, after the acid number of resin is less than 15mgKOH/g, except cooling discharge after solvent.
Epichlorohydrin resin performance:Colourless transparent liquid;Acid number:8.99mgKOH/g;Solids 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 Fat, bicarbonate KHCO3With solvent 1-Methyl-2-Pyrrolidone (NMP), plus catalyst cetyl ammonium bromide, CO is passed through2Afterwards 100 DEG C are risen to, 9h is incubated, weak yellow liquid is obtained, cool filtering and discharging.
Carbonic ester resin performance:Weak yellow liquid;Cyclocarbonate radical content 24%, solids 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 than biography PU unite more preferably.

Claims (10)

1. the method for polynary carbonic ester resin is prepared under a kind of normal pressure, it is characterised in that comprise the following steps:
1) preparation of epichlorohydrin resin:Acid anhydrides, polyalcohol and the first solvent are mixed, 90-120 DEG C is warming up to, 3-5h is incubated, added Simultaneously epoxychloropropane is added dropwise in first catalyst, is incubated 6-8h, after the acid number of resin is less than 15mgKOH/g, cooling discharge;
Described polyalcohol is 2,4- diethyl -1,5-PD, BDO, trimethylolpropane, double trihydroxy methyls third One or both of alkane, pentaerythrite and bipentaerythrite thing mixed above;
Described acid anhydrides is one or both of phthalic anhydride, trimellitic anhydride and pyromellitic dianhydride thing mixed above;
Described catalyst is tetraethylammonium bromide, TBAB, triphenylphosphine, tetramethyl ammonium chloride and benzyl triethyl ammonium One or both of ammonium chloride thing mixed above;
2) preparation of polynary carbonic ester resin:The epichlorohydrin resin, carbonic acid class salt and the second solvent are mixed, second is added and urges Agent, is passed through CO2After rise to 80-110 DEG C, permanent alternating temperature is incubated 5-9h, obtains weak yellow liquid, and cool filtering and discharging;
Described carbonic acid class salt is one or both of carbonate and bicarbonate thing mixed above;
During the second described catalyst is TBAB, 18- crown-s 6, LiBr, KI and cetyl trimethylammonium bromide One or more kinds of mixtures.
2. the method for polynary carbonic ester resin is prepared under the normal pressure according to claim, it is characterised in that:With quality hundred Divide meter, the raw material composition for preparing epichlorohydrin resin is:Acid anhydrides 38-45%, epoxychloropropane (ECH) 24-31%, polyalcohol 7- 21%, the first catalyst 0.1-0.5%;Remaining is solvent.
3. the method for polynary carbonic ester resin is prepared under the normal pressure according to claim, it is characterised in that:With quality hundred Divide than meter, preparing raw material composition in polynary carbonic ester resin is:Epichlorohydrin resin 40-55%, bicarbonate 28-40%, second Catalyst 0.5-1.5%;Remaining is the second solvent.
4. the method for polynary carbonic ester resin is prepared under the normal pressure according to claim, it is characterised in that:Described One solvent is one or both of ethyl acetate, butyl acetate, toluene, dimethylformamide (DMF) and methyl iso-butyl ketone (MIBK) Thing mixed above.
5. the method for polynary carbonic ester resin is prepared under the normal pressure according to claim, it is characterised in that:Described Two solvents are one in dimethyl sulfoxide (DMSO) (DMSO), dimethylformamide (DMF), 1-Methyl-2-Pyrrolidone (NMP) and acetonitrile Plant or two or more mixtures.
6. the method for polynary carbonic ester resin is prepared under the normal pressure according to claim, it is characterised in that:The carbonic acid Hydrogen salt includes NaHCO3Or KHCO3;The carbonate includes K2CO3Or Na2CO3
7. the method for polynary carbonic ester resin resin is prepared under the normal pressure according to claim, it is characterised in that:It is described Epichlorohydrin resin is transparent viscous liquid, and acid number is less than 15KOH/g;Solids content 65-85%, viscosity is 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 methods described, and 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 Solids content 40-70%, viscosity is 20-600mPas at 25 DEG C.
9. application of the polynary carbonic ester resin in metal protective coating described in claim 8.
10. it is characterized in that according to claim 9:The coating contains polynary carbonic ester resin and polyamine curing agent;Institute The polynary carbonic ester resin stated and polyamine curing agent mol ratio cyclic carbonate ester:NH2=1:0.90‐1.5;Described polyamine Curing agent is one kind in hexamethylene diamine, IPD, triethylene tetramine, polyetheramine, polyethyleneimine and TEPA Or a variety of mixtures.
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CN109824881A (en) * 2019-01-30 2019-05-31 华南理工大学 Fast preparation method and application under a kind of polynary carbonic ester resin and its normal pressure
CN109824881B (en) * 2019-01-30 2020-08-18 华南理工大学 Multi-cyclic carbonate resin and rapid preparation method and application thereof under normal pressure
CN110511717A (en) * 2019-10-12 2019-11-29 广东莱尔新材料科技股份有限公司 A kind of wafer with protection film adhesive and preparation method thereof
CN110511717B (en) * 2019-10-12 2021-05-04 广东莱尔新材料科技股份有限公司 Adhesive for wafer protective film and preparation method thereof
CN111471174A (en) * 2020-05-14 2020-07-31 苏州欧纳克纳米科技有限公司 Self-drying water-based non-isocyanate polyurethane
CN114773938A (en) * 2022-04-20 2022-07-22 史丹龙涂料(常州)有限公司 Environment-friendly anti-corrosion quick-drying paint and preparation method thereof
CN115260748A (en) * 2022-09-26 2022-11-01 扬州景怡医疗科技有限公司 Breathable high-polymer fixing splint and preparation method thereof
CN115260748B (en) * 2022-09-26 2023-09-12 扬州景怡医疗科技有限公司 Breathable polymer fixing splint and preparation method thereof

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