CN1175265A - Epoxy resin composition capable of cure at low temperature - Google Patents
Epoxy resin composition capable of cure at low temperature Download PDFInfo
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- CN1175265A CN1175265A CN 95197587 CN95197587A CN1175265A CN 1175265 A CN1175265 A CN 1175265A CN 95197587 CN95197587 CN 95197587 CN 95197587 A CN95197587 A CN 95197587A CN 1175265 A CN1175265 A CN 1175265A
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Abstract
An epoxy resin which is a reaction product of a polyepoxy and a polyol which contains both epoxy groups and terminal phenolic hydroxyl groups of at least 0.2 weight percent having added thereto an epoxy novolac having an epoxy founctionality greater than two. The epoxy resin is suitable for use as a power coating exhibiting lower melt viscosity than prior art resins of similar composition. The epoxy resin exhibits higher Tg/softening point than prior art resins of similar viscosity. A power coating prepared from the resin may be used on temperature sensitive substrates.
Description
The present invention relates to Resins, epoxy, prepare the method for Resins, epoxy and contain the composition of Resins, epoxy.
Because its physics and chemical property, such as chemical resistance of concrete, excellent adhesion, good solubility-resistence and hardness to various matrixes, Resins, epoxy has wide industrial application, comprises the coating of the various matrixes such as metal and the preparation of building and electric lamination.In many application, such as the coating of container (" can " etc.) inwall, Resins, epoxy is to use with solution in the organic solvent or aqueous dispersions.Do not use the powder coating of solvent to prepare by Resins, epoxy yet.
The molecular weight of Resins, epoxy influences the physical properties of resin usually, for example the physics and the chemical property of the softening temperature of Resins, epoxy, melt viscosity and soltion viscosity and the solidifying product that made by them.High molecular expoxy resin generally can strengthen toughness.
High molecular weight resin is such as the polyepoxide of dihydroxyphenyl propane diglycidyl ether and reaction product (so-called " pre-poly epoxy resin ") such as the polyphenol of dihydroxyphenyl propane.Prepolymerization reaction takes place between epoxy group(ing) and phenolic hydroxyl group, forms beta-hydroxy, has expanded the chain length of molecule thus.Prepolymerization reaction attaches crosslinking reaction.
The pre-collecting process of Resins, epoxy generally is such process, at first polyphenol is reacted to obtain polyepoxide, the preparation low-molecular-weight epoxy resin with Epicholorohydrin and alkali metal hydroxide in the presence of catalyzer.After this initial polyepoxide reaction product further forms the high-molecular weight material with the reaction of the polyphenol of additional content again.In the routine techniques of preparation Resins, epoxy, the reaction of polyepoxide and polyphenol generally proceeds to complete transforming degree, makes final pre-poly epoxy resin contain the remaining phenolic hydroxyl group of low relatively amount.For example by the EEW (epoxy equivalent (weight)) of dihydroxyphenyl propane and dihydroxyphenyl propane diglycidyl ether preparation for the Resins, epoxy of 500-700 contains the phenolic hydroxyl group that is lower than 800ppm, the transformation efficiency that its representative prepares the phenolic hydroxyl group that adopts in Resins, epoxy is higher than 98%.The high molecular expoxy resin of EEW＞2000-4000 contains the phenolic hydroxyl group that is lower than 2500ppm usually, and it represents the phenolic hydroxyl group transformation efficiency greater than 95%.
Known that any remaining phenolic hydroxyl group in the pre-polymerization resin can make the viscosity instability of resulting resin compound, particularly when elevated temperature.As control because a kind of method that the resin viscosity that causes of unreacted phenolic hydroxyl group descends, US3,842,037 suggestions are when the phenolic hydroxyl group at least 85% that adopts in the prepolymerization reaction, more preferably at least 95% reacted back adding strong inorganic acid.
In addition, in the other method of preparation high molecular expoxy resin, US 3,352,825 point out, in the presence of the catalyzer such as the alkali metal salts or ammonium salt of monobasic mineral acid, with dihydric phenol and excess epichlorohydrin reaction, the free hydroxyl group content that forms every mole of said dihydric phenol is the intermediate of 0.2-0.5 scope phenolic hydroxyl group.Remove remaining Epicholorohydrin then, with rear center body condenses caustic alkali dehydrohalogenation, the free phenolic hydroxyl group and the epoxy reaction of formation simultaneously on the spot.
Unfortunately, the molecular weight of increase Resins, epoxy has generally also increased the melt viscosity and the soltion viscosity of resin.The increase of this melt and soltion viscosity makes as the application of the powdered epoxy of topcoating difficult more.The resistance to flow of the powdered granule that the viscosity representative is coalescent.Surface tension is provided by the mobile motivating force that provides of coating.Mobile reduction may make coating produce " skin short of money " outward appearance (P.G.de lange, the film forming of powder-type coating and rheology, 56 coating technology magazines (Film formation andRheology of Powder Coatings, 56, J.Coatings Technology) No.717, in October, 1994, pp23-33).
Can reduce the melt of Resins, epoxy of given EEW and a kind of method of soltion viscosity is that reaction product contains the chainpropagation that the method for epoxy group(ing) and terminal hydroxy group is regulated pre-polymerization resin with the reaction product of preparation polyepoxide and polyvalent alcohol.Prior art US 4,722,981 has narrated the Resins, epoxy with epoxy group(ing) and terminal hydroxy group, epoxy group(ing) and terminal hydroxy group amount separately is at least 0.25% (weight), and said weight percentage is based on Resins, epoxy reaction product total weight.This resin can be used as starting raw material of the present invention.
Yet, although the resin of prior art US 4,722,981 be have improved, the characteristic limitations of this resin in formulation for coating material its application, it can not be used to stand the severe relatively condition of cure of powder coating.
For feasible economically, powder coating existing and prior art requires 160-200 ℃ of curing.Lower solidification value can make powder coating be used for thermally sensitive matrix, such as the thermoplastics of timber.
Can prepare the coating system of solvent, its curing does not need elevated temperature.Therefore the temperature-sensitive matrix can apply with the epoxypaint system that solvent is arranged.Solvent substrate is that desired volatile organic solvent is environmentally harmful by identification.Basic non-volatility component and can be on to the temperature sensitive matrix solidified powder coating provide and reduced the chance of distributing solvent to environment, yet still can on the temperature-sensitive matrix, provide effective coating.
Existing epoxypaint system can be solidified through considerable time being lower than under 160 ℃ the temperature, and promptly bisphenol A epoxide resin coating can solidify through 20-22 minute at 120 ℃ with bisphenol A-type phenol stiffening agent.The principle of generally following is that the coating that the viscosity under the melt temperature is lower can obtain binding property preferably than other similar resin (P.G.de Lange document); Low-molecular-weight resin and stiffening agent generally present lower viscosity than similar high molecular weight resin and stiffening agent.
But solution unsuitable be coated with wet and therefore coating can not only solve the bonding very poor of matrix with reduction molecular resin amount.The negative function that the molecular weight that reduces will produce other.Reduce softening temperature and glass transition temperature Tg that molecular weight generally also reduces resin.The softening temperature that reduces can make the resin particle when storing lump and be bonding, reduce the storage life of the powder coating that obtains, and the generation smoothness can not satisfactory coating.
What need now is to have the coating of low-viscosity epoxy powder coating to provide under low solidification value on thermally sensitive matrix, and the sufficiently high softening temperature/Tg that keeps resin Composition simultaneously is to obtain suitable storage life.Certainly also must satisfy other requirement of coating, such as good flowability (not having " tangerine peel " outward appearance), good snappiness, high gloss and erosion resistance.This coating is not precluded within on the non-temperature sensitive matrix and uses, and it can realize qualitative further improvement such as mobile and outward appearance.
The invention provides the Resins, epoxy that is used under low solidification value, having low viscous powder coating; it has good flowability and coating wettability; glossy and have high-flexibility to become reconciled defencive function also provides the softening temperature/Tg that is enough to provide suitable storage life.More particularly, the present invention is the Resins, epoxy that comprises polyepoxide and polyol reaction product, wherein this reaction product contains epoxy group(ing) and end phenolic hydroxyl group, the amount of epoxy group(ing) and end phenolic hydroxyl group at least respectively is about 0.2% (weight), said weight percentage is based on Resins, epoxy reaction product total weight, its improvement be included in add that Mn is at least 450 after first step of reaction, Mw/Mn than greater than 1.05, the epoxy functional degree is greater than 2 epoxidization phenolic resin.
In one embodiment, the present invention one comprises the Resins, epoxy of polyepoxide and polyol reaction product, wherein reaction product contains epoxy group(ing) and end phenolic hydroxyl group, the amount of epoxy group(ing) and end phenolic hydroxyl group at least respectively is about 0.2% (weight), and said weight percentage is based on Resins, epoxy reaction product total weight; Its improvement comprises and adds the epoxy functional degree greater than 2 epoxidization phenolic resin.
In another embodiment, the present invention is a method of producing composition epoxy resin, and it is included under the isothermal condition polyol reactant with formula I
In the formula, A is independently of one another-S-,-S-S-,-C (O)-,-S (O)-,-S (O)
2-, contain the bivalent hydrocarbon radical of 1-8 carbon atom or contain the alkyl or a covalent linkage of oxygen, sulphur or nitrogen, A also can be
X is hydrogen, halogen or the alkyl that contains 1-4 carbon atom independently of one another, and the mean value of n is 0-5, the polyol reactant of preferred 0-2 or formula II
In the formula, respectively do for oneself hydrogen or the alkyl of 1-4 carbon atom is arranged of R, Y is independently of one another for hydrogen, chlorine, bromine or the low alkyl group of 1-4 carbon atom is arranged, and the mean value of m is greater than 0 to 10 or the composition mixture of formula I and formula II and the epoxy reaction thing III of formula III
In the formula, described in each A and X such as the preceding formula I, the mean value of n be 0-4 or with the epoxy reaction thing of formula IV
In the formula, R, Y and m are as mentioned above, referring to formula II or with the many glycidyl ethers (such as polypropylene glycol diglycidyl ether) of polyglycol or the mixture reaction of the many glycidyl ethers of three (phenol) methane or triazine triglycidyl group ether (for example triglycidyl isocyanurate) or these epoxy reaction things, making epoxy group(ing) component and hydroxy component ratio is 0.1: 1-10: 1, also comprise the catalysts that an inhibited reaction carries out, its resin when predetermined reaction conversion ratio is had at least about the terminal hydroxy group of 0.2% (weight) with at least about the end epoxy group(ing) of 0.2% (weight).
Compare with the analogous composition of no epoxidation resol, resulting coating composition has presented low viscosity when fusion.Therefore resin combination has obtained having improved flowability thereby big wettability has been arranged and improved fusible powder coating is arranged thus.
Resins, epoxy of the present invention has many advantages than the Resins, epoxy of routine, and its transforming degree is not reasonably having further significant prepolymerization reaction generation (often being referred to as " the full conversion ") and is being substantially free of terminal hydroxy group in the time between epoxy group(ing) and terminal hydroxy group.When with transform resin entirely by the similar prior art of forming relatively the time, the melt viscosity of resin of the present invention and soltion viscosity all have reduction.For to the resin that given melt viscosity is arranged under the fixed temperature, resin of the present invention provides higher Tg, and it and softening temperature are closely related, and therefore transforming resin entirely than the prior art that similar melt viscosity is arranged under uniform temp has longer storage life.
Because this resin contains epoxy group(ing) and terminal hydroxy group, they can constitute easily single-component system uniformly, do not need additional stiffening agent, and this resin only need add promotor just can be mixed with powder coating.
Epoxy-resin coating composite of the present invention comprise per molecule on average contain more than 1, preferred 1.8 or more a plurality of can with the polyvalent alcohol of the hydroxyl of polyepoxide reaction.This polyvalent alcohol can be saturated or undersaturated aliphatic series, cyclic aliphatic, aromatics or heterogeneous ring compound, and they can be replaced by one or more non-interference substituents (such as halogen atom or ether).In general, polyphenol is a preferred polyhydric alcohols.The polyphenol that advantageously adopts when preparation Resins, epoxy is the polyphenol with following structural formula I representative:
In the formula, A is a covalent linkage independently of one another ,-S-,-S-S-,-C (O)-,-S (O)-,-S (O)
2-, contain the bivalent hydrocarbon radical of 1-8 carbon atom or contain the alkyl of oxygen, sulphur or nitrogen or following composition:
In the formula, X is hydrogen, halogen or the alkyl that contains 1-4 carbon atom independently of one another, and the mean value of n is 0-5, preferred 0-2,
And the phenol formaldehyde condensation resin of formula II:
In the formula, R is hydrogen or the alkyl that 1-4 carbon atom arranged independently of one another, and Y is hydrogen, chlorine, bromine or the low alkyl group that 1-4 carbon atom arranged independently of one another, and the mean value of m is 0-10.Also can use the mixture of one or more polyphenol.
Preferred polyphenol is that A is that the bivalent hydrocarbon radical of 1-8 carbon atom, mean value that each X is hydrogen, n are 0-0.5 and the polyphenol compound that is preferably 0 general formula I.Most preferred polyphenol is 2, and two (4-hydroxyphenyl) propane of 2-often are called dihydroxyphenyl propane (BPA).
Used initial reaction polyepoxide component is the compound with two or more epoxy group(ing) in Resins, epoxy preparation of the present invention.Polyepoxide can be saturated or undersaturated aliphatic series, cyclic aliphatic, aromatics or heterogeneous ring compound, and they can by one or more non-interference substituents (such as halogen atom or ether, they the preparation resin condition under not with epoxy group(ing) or hydroxyl reaction) replace.With polyol reaction can be monomer or polymkeric substance with the polyepoxide component that forms resin.
The illustrative example of useful Resins, epoxy is described in the following document: H.Lee and K.Neville, Resins, epoxy handbook (The Handbook of Epoxy Resins), McGraw-Hill, New York, 1967, pp 4-35 to 4-56.
Interested especially polyepoxide comprises many glycidyl ethers of the bis-phenol of general formula III in the specific embodiments practice:
In the formula, described in A and X such as the following formula I, the mean value of n is 0-4, preferred 0-2,0-0.5 most preferably); Resol contract glyceryl ether, i.e. phenol-aldehyde condensate of formula IV more:
(in the formula R, Y and m as mentioned above, referring to formula II); The many glycidyl ethers of polyglycol (such as polypropylene glycol diglycidyl ether); And many glycidyl ethers of tris-phenol or triglycidyl isocyanurate.The mixture of one or more polyepoxides also is suitable for adopting.Preferred polyepoxide is many glycidyl ethers, particularly dihydroxyphenyl propane diglycidyl ether of the bis-phenol of liquid state; The many glycidyl ethers of tetrabromobisphenol, particularly tetrabromo-bisphenol diglycidyl ether and their mixture.
Polyepoxide and polyvalent alcohol to have utilization should make the ratio of hydroxyl equivalent number in epoxide equivalent number and the polyvalent alcohol in the polyepoxide be 0.1: 1-10: 1.The preferred polyepoxide that adopts is 0.3 with the epoxide equivalent of polyol component with the hydroxyl equivalent ratio: 1-5: 1, more preferably 0.3: 1-2: 1.The polyepoxide of favourable employing and the relative proportion of polyol component will be decided by many factors, comprise the polyepoxide that adopted and the kind of polyvalent alcohol, and by the desired character of Resins, epoxy of their preparations.
The preparation of resin is in the presence of the catalyst for reaction between polyvalent alcohol hydroxyl and the polyepoxide epoxy group(ing) with under the sufficiency that forms required resin polyvalent alcohol to be contacted with polyepoxide.Only it is preferred reacting, and does not promptly have any reaction diluent or solvent.
Can the described catalyst for reaction of catalysis be well known in the art, for purpose of the present invention provides following reference.Illustrative catalyzer is described in US 2,633,458,2,658,855,3,337,406,3,694,407,3,948,855,4,389,520,4,354,015 and 3,477,990 and Resins, epoxy handbook (The Handbook of Epoxy Resins) (H.Lee and K.Neville, pp 11-13 to 11-23) in.The representative of described catalyzer is secondary amine and tertiary amine, preferably the tertiary amine such as dimethyl benzylamine, triethylamine and diethyl benzylamine; Alkali metal hydroxide, for example potassium hydroxide; Quaternary ammonium compound such as tetraalkylammonium halide, for example tetramethylammonium chloride; And phosphine is with quaternary alkylphosphonium salt, such as triphenyl phosphine and acetate Yi base triphenyl phosphonium.
The typical amounts of catalyzer is a convention amount.This tittle changes according to used special catalyst, polyepoxide and polyvalent alcohol, but its preferably the 0.001-1% (weight), the catalytic amount that more preferably adopts of polyvalent alcohol and many glycidyl ethers component gross weight be 0.01-0.25% (weight), said weight percentage is based on polyvalent alcohol and polyepoxide total weight.
The reaction of polyvalent alcohol and polyepoxide component can be carried out in the presence of reaction diluent, though this is not preferred.As adopt reaction diluent, it preferably polyvalent alcohol and polyepoxide component solvent or with they miscible solvents.Can adopted representative solvents comprise various glycol ethers (such as ethylene glycol monomethyl ether or propylene glycol monomethyl ether) and their ester (such as ethylene glycol monoethyl ether acetate), ketone (such as methyl iso-butyl ketone (MIBK), methylethylketone and acetone) and aromatic hydrocarbon (such as toluene, dimethylbenzene or their mixture).During employing, the general consumption of liquid organic reactant thinner is the 5-300% of polyvalent alcohol and polyepoxide gross weight.
Being reflected under the elevated temperature of polyvalent alcohol and polyepoxide is favourable, and preferred temperature is 60-200 ℃, more preferably 100-180 ℃.Reaction proceeds to desired transformation efficiency, can survey parameter (such as the residual epoxy base in the resin and terminal hydroxyl content or melt viscosity) by monitoring and determine that the terminal point that is reflected at requirement stops effectively.
The prediction resin reaches the method that makes things convenient for of the approximate time of desired characteristic and comprises, react under basic isothermal condition with laboratory scale, in different various time termination reactions, and measure physics or chemical parameters (such as melt viscosity and residual hydroxyl content) comes the assaying reaction degree with the known usual method of art technology expert.
When reaching desired degree of conversion, stop any method of further reaction all can adopt effectively.Fully to reduce the reaction (if present) that makes continuation not obvious and stop reaction can not influence product or its treatment characteristic nocuously the time effectively when the speed of reaction of hydroxyl and epoxy group(ing).Preferably sufficient reacting is stoped the viscosity make resin to keep basic constant or along with the prolongation of time has only limitedly and increases, for example can the quenching reaction mixture when reaching desired degree of conversion with stopped reaction.But the quenching rapidly of reaction mixture must carefully be carried out with prevention resin caking or agglomerating and stop the big solid mass of resin formation and can't use.
The method that makes things convenient for of reaction mixture comprises solubilizing agent in mixture, with the diluted mixture thing and reduce its temperature.The amount that adds organic solvent depends on that temperature of reaction and reaction are by effective terminated temperature.When resin when using with solution subsequently, in reaction mixture, add organic solvent and be preferred especially the selection.
Stop the preferred method of reaction to comprise that adding a kind of material in reaction mixture continues reaction to stop effectively,, stop thus and continue reaction between polyvalent alcohol and polyepoxide such as making catalyst deactivation or blocking reaction mechanism.
Have now found that the acid anhydride of strong inorganic acid and organic acid and said acid and ester (comprising half ester and part ester) are effective especially as reaction arrester.The meaning of " strong acid " speech is that the pKa value is lower than 4, preferably is lower than 2.5 organic acid.Representational reaction arrester comprises the mineral acid such as spirit of salt, sulfuric acid and phosphoric acid, such as phosphoric anhydride (P
2O
5) and so on inorganic acid anhydrides, inorganic acid ester such as methyl-sulfate, organic acid such as alkyl, aryl and the sweet-smelling alkyl sulfonic acid of alkyl, aryl and aralkyl and replacement (such as tosic acid and Phenylsulfonic acid), and the stronger organic carboxyl acid such as trichoroacetic acid(TCA), alkyl ester with said acid, such as alkyl tosylate, for example methyl tosylate and ethyl ester and methyl mesylate.The example of the strong organic acid acid anhydride that can be adopted by the present invention is the tosic acid acid anhydride.In these reaction arresters, the alkyl ester of alkyl sodium sulfate ester, aryl or aralkyl sulfonic acid and said acid is that preferred the selection used.The present invention most preferably adopt as reaction arrester be alkyl tosylate, particularly methyl tosylate or ethyl ester.
The amount that adds the reaction arrester in the reaction mixture is decided by the specific hold back agent that is adopted and prepares the catalyzer that resin adopted.In general, the prevention dosage of adding should be enough to overcome the catalytic activity of catalyzer.Preferably the catalyzer that is adopted whenever amount adds at least 0.9, more preferably at least 2 normal hold back agents.Though add the cost that the maximum of hold back agent is decided by desired resin properties and adds excessive hold back agent in reaction mixture, the preferred add-on of hold back agent is whenever the amount catalyzer is no more than 5 equivalents in the reaction mixture.
The temperature of the also available control reactive component of resin of the present invention prepares.In being arranged, the extruding machine of temperature-controlled area reacts the additional temperature control that can reach to reactive component.Can fully heat the catalytic activity of any catalyzer that exists with destruction with the high-temperature zone to reactive component.In addition, hold back agent can be added reactive component to interrupt activity of such catalysts or to make the stopping of reaction of reactive component with other mechanism.With the advantage that reduces the temperature termination reaction is that resin does not contain and adds the desired hold back agent of hold back agent termination reaction.
Reaction is a terminated when resulting resin contains the epoxy group(ing) of required amount and terminal hydroxy group.In the present invention, resin will contain the epoxy group(ing) and the terminal hydroxy group of at least 0.2% (weight) respectively.The meaning of " epoxy group(ing) " speech is that equivalent weight percentage ratio is arranged is the group of 43 following structural formula:
The meaning of " terminal hydroxy group " is that equivalent weight is 17 terminal hydroxy group.
The weight percentage of epoxy group(ing) can be by US 4,722 in the Resins, epoxy, and disclosed method is measured in 981.
These weight percentage also can be considered the equivalents of epoxy group(ing) and hydroxyl in the per kilogram resinous reaction product.Through measuring, in the resin that per kilogram is produced, the epoxy group(ing) of 0.2% (weight) is about 0.0465 epoxide equivalent.Similarly, in the resin that per kilogram is produced, the hydroxyl of 0.2% (weight) is about 0.12 hydroxyl equivalent.
The hydrolyzable chloride of resin generally is lower than 1%, usually is lower than 0.5%, based on Resins, epoxy reaction product total weight.Can allow but based on Resins, epoxy reaction product total weight, hydrolyzable chloride reaches 5% (weight), preferably be no more than 2% (weight).The amount of measuring the hydrolyzable nitride for purpose of the present invention adopts the method in the following document: Resins, epoxy handbook (The Handbook of Epoxy Resins) pp.4-29 and 4-30 (table 4-23).
Though the best epoxy group(ing) and the terminal hydroxy group amount that are contained in the resin depend on desired resin properties, the soltion viscosity of resin for example, but resin preferably contains the terminal hydroxy group of the epoxy group(ing) and at least 0.2% (weight) of at least 0.5%, more preferably at least 1% (weight), and said weight percentage is based on the resin total weight.In the ordinary course of things, resin preferably include be lower than 20%, more preferably less than the epoxy group(ing) of 12% (weight) and be lower than 10%, more preferably less than the terminal hydroxy group of 7% (weight).
In the fs of preparation resin, control the transformation efficiency of polyvalent alcohol and polyepoxide component, make resin contain the epoxy group(ing) and the hydroxyl of required amount.This transformation efficiency is decided by the amount of used polyvalent alcohol and epoxide.Advantageously, at least 45% of the substoichiometric component of existence and at the most 95% react.If use two components of equivalent, two components all have at least 45% also 95% to react at the most so.Preferably at least 50%, more preferably 55%, and at the most 95%, more preferably at the most 90%, most preferably 85% substoichiometric component or equivalent reactant (as the case may be) react at the most.
The number-average molecular weight of resin is decided by the end-use of desired resin and physics and the chemical property that end-use requires.The molecular weight of resin preferably is lower than 10,000.Resin has that to be lower than 4000 molecular weight be preferred, most preferably is lower than 2000, and more preferably greater than 300, most preferably greater than 500.
In the present invention's practice, polyepoxide and polyvalent alcohol can be carried out pre-polymerization with (optionally) polyprotonic acid, in a reactions steps, finish and (form the resin that has only epoxy group(ing) or have only terminal hydroxy group thus, be decided by to adopt any excess reactant), after this again with polyvalent alcohol or polyepoxide component reaction, form resin.The pre-polymerization of epoxide and diprotic acid is discussed among 722,981 embodiment 18 to some extent at polymer science progress (Advancesin Polymer Science) (Madec, P-J etc., 71 (1985) 153-224) and US4.
From second step of reaction that the fs reaction product that also has unreacted hydroxyl and epoxy group(ing) begins, in resin, added average functionality greater than 2 compound.This component reduced under the solidification value viscosity and with the reaction of fs.Thereby the adding component of subordinate phase can be described to " reactive diluent ".
Because the resin in the preparation of first step of reaction provides hydroxyl and epoxy-terminated, the crosslinked compound that is suitable for that adds in subordinate phase can be a hydroxyl reactive, also can be epoxy reaction.
As the hydroxyl reactive compound that is suitable for adding in subordinate phase is many glycidyl ethers of the phenol described in the aforementioned formula IV-aldehyde condensation resins.
For the many glycidyl ethers of this class, the scope of m is answered average out to＞0-5.0, more preferably 0.5-4.5.The mixture that formula III and I (scope of m and n as specified) mix many glycidyl ethers also is fit to.In this class mixture, the hydroxyl reactive component that subordinate phase adds at least 5%, preferred 12%, more preferably 25% average functionality is favourable greater than 2, the average functionality of the basic surplus hydroxyl reactive component that subordinate phase adds can be 2 or littler, but greater than 1.2.In subordinate phase, thinner or solvent can be arranged.Favourable amount of diluent is lower than 50% (weight) of gross weight.
As the epoxide-reactive compound that is suitable for adding in this subordinate phase, the described polyphenol of formula II is fit to.The m scope of this class polyphenol answers＞0 to 5.0, preferred 0.5-4.5.The polyphenol mixture of formula I and II (scope of m and n as specified) also is fit to.In this class mixture, the average functionality of the epoxide-reactive component that have at least 10%, preferred 20%, more preferably 25% subordinate phase adds is favourable greater than 2.In subordinate phase, thinner or solvent can be arranged.Favourable dilution dosage is lower than 50% (weight) of subordinate phase composition gross weight.
As the Resins, epoxy that can solidify at lesser temps, its characteristic improves to some extent than prior art, particularly as coating, some best specific embodiments of the present invention has proved its obvious advantage.
After further stage termination reaction, resin can be mixed with many different compositions and use in various end-uses.For example resin can with promotor and optionally other assistant agent (such as flow control agent) mix and form powder paint compositions.Though can in resin, add stiffening agent,, not add stiffening agent and also can solidify owing to contain unreacted epoxy groups and unreacted terminal hydroxy group in the resin.
Normally used stiffening agent, catalyzer and promotor can be used for toner coating composition of the present invention in the powder paint compositions based on Resins, epoxy.This class stiffening agent and promotor are well-known in the art, for purpose of the present invention provides reference.Representative promotor comprises monocarboxylic tin salt, such as stannous octoate and the inferior tin of lauric acid; Various an alkali metal salts are such as lithium benzoate; Some heterogeneous ring compound is such as imidazoles and benzimidazole compound and salt thereof; Compounds, such as quaternary ammonium with quaternary phosphonium compound; And tertiary amine, phosphine and phenol carbamate.
The preferred accelerators that is used to prepare the powder coating prescription is at room temperature to be solid promotor to comprise imidazoles, and the imidazoles that replaces of alkyl particularly is such as methylimidazole; Solid phosphine compound or amine are such as triphenyl phosphine, quaternary phosphine and quaternary ammonium compound.
Best promotor usage quantity has difference according to employed particular promoter in the preparation powder paint compositions.Preferred accelerator level is based on the heavy 0.01-5% (weight) of resin, more preferably 0.02-3% (weight).
The stiffening agent that representational selection is used is phenol aldehyde type stiffening agent and the british patent specification No.1 such as phenol type or cresols type phenolic varnish class, phenol aldehyde type stiffening agent described in 429,076, dicyanodiamide, acid anhydrides (such as trimellitic acid 1,2-anhydride), sour functional polyester and hydrazides (such as adipic dihydrazide and m-phthalic acid two hydrazides).As use stiffening agent, its consumption generally to be based on the 1-50% (weight) of resin gross weight.
Have found that, the resin that the subordinate phase as powder coating that is fit to is reacted, the equivalents of its per kilogram epoxy group(ing) is 1.54-2.1, maximum epoxy equivalents is 5.9.Too much epoxy equivalent (weight) number produces low softening temperature.Preferred epoxide equivalent scope is that the per kilogram resin is greater than 4.1.Most preferably changing into epoxy in any epoxy group(ing) derives and is per kilogram resin 5.4-5.9 epoxide equivalent before the base.This resin contains the end phenolic hydroxyl group of 0.2-1.5 equivalent/kilogram.Find that now it is necessary that not only above-mentioned hydroxyl and epoxy group content scope are particularly conducive in the Resins, epoxy of solution paint prescription in the controlled production of resins of transformation efficiency, and surprising be that at least a portion epoxy group(ing) at the controlled resin of these transformation efficiencys is when further changing into epoxy and deriving base (such as salmefamol or phosphate-based), compare with the resin that epoxy-terminated nothing further transforms, significantly reduce its set time, kept good resin and coating property simultaneously.
Generally, the epoxy group(ing) of the controlled resin of transformation efficiency can change into any epoxy that the does not influence curing reaction functional group that derives.Though the present invention is not limited by this theory, believe that the hydrolysis reaction of the water of epoxy group(ing) and adding has formed salmefamol.Therefore the adding of water is that epoxy group(ing) is converted into the derive method of base of suitable epoxy easily.In this regard, the equivalents of epoxy group(ing) will determine to form the derive amount of basic needed water or other reactant of salmefamol and other possible type epoxy.The general excessive water that uses based on the 0.5-20% (weight) of resin gross weight, preferred 1-10% (weight).
The reaction of resin and water and acid also can be used to transform epoxy group(ing).This is the conversion of epoxy group(ing) to salmefamol and acid esters in theory, and has the group that epoxy group(ing) is derivatized to other type, but the present invention is not limited by this theory.The general consumption of water and acid is the acid of 0.2-10% (weight).These weight percentage are based on the resin total weight that added water and acid.The weight percentage of preferred water and acid is respectively 0.5-3% (weight) and 0.2-2% (weight).
In putting into practice a method of the present invention, the epoxy group(ing) of the controlled resin of transformation efficiency and water and phosphoric acid reaction.In this specific embodiments, the amount of water and phosphoric acid (preferably phosphoric acid) should obtain balance at utmost to increase monoesters and at utmost to reduce by three esters.The general discovery, when according to said method in the controlled resin of transformation efficiency, using phosphoric acid, its add-on should be based on the heavy 0.1-3% (weight) of resin, preferred 0.2-1.5% (weight), and the water yield that adds simultaneously should be based on the heavy 0.2-10% (weight) of resin, preferred 0.5-3% (weight).
In another specific embodiments of the present invention, in first step, prepare the reaction arrester of the controlled resin of transformation efficiency with a certain amount of water and acid (preferred phosphoric acid) conduct.The amount of water that adds and acid surpasses the prevention polyvalent alcohol and polyepoxide reaction aequum of being instructed, this excessive water and acid then can with the epoxy group(ing) formation epoxy of the controlled resin of the transformation efficiency base of deriving.The mixture of preferred above-mentioned these groups comprises the ester class of salmefamol class and phosphoric acid.When by this pattern inhibited reaction and when epoxy group(ing) changed into epoxy and derive base simultaneously, used acid amount be based on the heavy 0.1-3% (weight) of resin, preferably 0.2-1.5% (weight).
Can find that the epoxy group(ing) with at least 30% changes into the epoxy base of deriving, can improve the solidification rate of resin and shorten desired total set time thus.Preferably greater than about 50% and most preferably all basically epoxy group(ing) all change into the epoxy base of deriving.Though this resin is substantially free of epoxy group(ing), still be known as Resins, epoxy from its source of students at this.Certainly, when in single step and/or by monoreactant, transforming, just there is no need to isolate the controlled resin of transformation efficiency of specific epoxy group content such as phosphoric acid when the prevention reaction with the epoxy group(ing) conversion.In these situations, within the scope of the invention, the epoxy radix that retains in the final resin product (if any words) and the epoxy basic existence of deriving be the symbol that the present invention puts into practice, and will produce improved resin.
In addition, behind the preparation resin, resin can be dissolved in organic liquid in order to using.The suitable organic liquid of the organic aqueous solution of preparation resin is decided by the particular case of resin and the amount of terminal hydroxy group in the resin and epoxy group(ing).In general, alcohol (such as propyl carbinol), glycol ethers (such as propylene glycol monomethyl ether) and its ester, ketone, fat or aromatic hydrocarbon (such as dimethylbenzene) and chloro fat and aromatic hydrocarbon are preferred the selections.
When the organic aqueous solution of preparation resin, using the stiffening agent that also can be dissolved in organic solution generally is ideal.This class stiffening agent is well-known in the art and provides reference for the object of the invention.Representative stiffening agent comprises that resol (such as the reaction product of phenol and excess formaldehyde) and other contain benzene derivative and the alkyl derivative and the amine aldehyde condensate (often being called aminoplastics (" aminoplast " or " aminoplastics ")) of methylol, and they are aldehyde and the condensation product of amine (such as trimeric cyanamide, urea and benzo guanamine) and their alkyl derivative.
The best consumption of stiffening agent is decided by many factors, comprises the end-use of organic aqueous solution and physics and the chemical property that said end-use requires.Preferred stiffening agent consumption is the 1-50% (weight) based on resin and stiffening agent gross weight.
In addition, adding small amounts of inorganic acid in organic aqueous solution usually is ideal as resin and stiffening agent catalyst for reaction.In general, preferred mineral acid is a phosphoric acid, and its consumption is based on the 0.1-5% of organic aqueous solution gross weight (weight).
The solids concn of making organic aqueous solution is decided by various factors, comprises the viscosity of gained solution requirement.Organic aqueous solution generally is mixed with and makes solids content high as far as possible, keeps enough low viscosity simultaneously again, is beneficial to use.Because resin presents than the conventional resin with identical curing properties lower soltion viscosity is arranged, the organic aqueous solution of resin generally can be prepared into than conventional resin organic aqueous solution higher solids content.The resin that for example is used for application of paints can be mixed with such organic aqueous solution, and it comprises resin and any stiffening agent of at least 40% (weight), based on the organic aqueous solution total weight.Preferred organic aqueous solution contains at least 50%, more preferably resin and the stiffening agent of 50-70% (weight).
Shown from the powder coating of resins of the present invention and advantageous property than prior art to have made this resin be particularly conducive to application of paints.This coating has formed the surface (seeing P.G.de Lange document) of uniformity well on matrix.
Shown its low viscosity under condition of cure well by resins powder coating of the present invention, in the fs reactant, added epoxidization phenolic resin and can obtain special more favourable low viscosity.
The curing of Resins, epoxy is decided by solidification value and set time.Resin of the present invention is that the prior art of finishing than similar composition of solidified, resin solidification takes shorter under the temperature condition lower than prior art.Moreover, shown the coating character consistent by the solidified coating composition of resins of the present invention, although it is a solidified under the solidification value of gentleness with prior art.Can solidified prior art resin exists under the resin solidification temperature of the present invention being similar to.Yet resin of the present invention has presented higher Tg/ softening temperature, and therefore long storage life is arranged.
Learn from the following examples and can find out these and other advantage more significantly.
Embodiment 1
In nitrogen atmosphere, in the presence of 1.4 weight part acetate Yi base San Ben Phosphonium, 2760 weight part dihydroxyphenyl propane diglycidyl ether are mixed with 1310 weight part dihydroxyphenyl propanes.Mixture is heated to 120 ℃ and temperature and is risen to 150 ℃ gradually, keeps 150 ℃ temperature 1-5 hour, and until reaching desired melt viscosity, this viscosity is determined as 1-6pas under 120 ℃.Under the viscosity of this requirement, in mixture, add 1 part of methyl tosylate and mixed 20-30 minute.Also optionally add flowing agent pigment, leveler or other batching when needing.With 930 parts be preheated to 90 ℃ Mn be 534 and the epoxidization phenolic resin of Mw/Mn=1.7 (5.2 equivalent) add in the mixture and remix 10-20 minute.
Content in the cooling reactor.Resin at room temperature is a solid.The character that records resin is as follows: epoxy equivalent (weight) 450; 77.6 ℃ of softening temperatures; Melt viscosity 2.5pas (120 ℃) and 0.4Pas (150 ℃); Number-average molecular weight (Mn) 900; Weight-average molecular weight (Mw) 2340; Molecular weight ratio (Mw/Mn) 2.6.
Embodiment 2-9
The step that embodiment 2 to 8 presses embodiment 1, the component of adding is shown in table 1.An extrusion machine is used in the preparation of embodiment 9, as described in embodiment 20-24.Prepared the resin that character shown in the table is arranged.
Embodiment 10 (the non-embodiment of the invention)
In the presence of 0.05 part of acetate Yi base San Ben Phosphonium, mix 67.9 parts of dihydroxyphenyl propane diglycidyl ether and 32.1 parts of dihydroxyphenyl propanes.Mixture is heated to 150 ℃ under mixing, allow be reflected at adiabatic continuation down 3 hours, until thinking dihydroxyphenyl propane complete reaction.Adiabatic reaction is with mixture heating up to 190 ℃.In this liquid mixture, add the epoxy functional degree then and be 3.6, Mn is 534 and the epoxidization phenolic resin of Mw/Mn=1.7, its amount has the composition of the content of epoxidization phenolic resin shown in the Table II with preparation.With composition cools to room temperature.The character of resin combination is shown in Table II.
Embodiment 11
Under nitrogen atmosphere, 22.36 parts of dihydroxyphenyl propane diglycidyl ether, 10.33 parts of dihydroxyphenyl propanes and acetate Yi base triphenyl phosphonium catalyzer (207ppm) are added in the reaction vessel.Under continuously stirring, reactant is heated to 120 ℃.Periodic sample is also measured the method for viscosity as the assaying reaction performance level.From the viscosity of the sample that takes out as can be known, after 6 hours, reached predetermined target viscosities.The carrying out that under continuously stirring, adds 0.008 part of methyl tosylate stopped reaction.Continue to stir 10 minutes.In reaction vessel, add 7.5 parts of Mn and be 534, Mw/Mn is 1.7 100 ℃ the epoxidization phenolic resin of being heated to.Composition stirs and takes out test after 3 hours.The performance of resin as shown in Table II.
Table I
| Component (weight part) | 2 * | 3 | 4 | 5 * | 6 * | 7 | 8 | 9 |
| The solid epoxy that contain 40% epoxy functional degree and be 3.6, Mn is 534, Mw/Mn is 1.7 epoxidization phenolic resin.The epoxy equivalent (weight) of said composition is 325. | 22 | |||||||
| No Mn is 534, the resin of the embodiment 1 of the epoxidization phenolic resin of Mw/Mn=1.7. | 44.0 | |||||||
| Solid epoxy, EEW=700-750 | 39.0 | |||||||
| Have that 18.6% epoxy functional degree is 3.6, Mn is 534, the solid bisphenol A epoxy resin 4-type of the epoxidization phenolic resin of Mw/Mn=1.7. | 50.3 | |||||||
| Epoxy equivalent (weight) is the pre-poly epoxy resin of solid dihydroxyphenyl propane of 495-526 | 25.4 | |||||||
| The vibrin of saturated carboxylic acidization (1) | 37.0 | 26.0 | 31.0 | |||||
| The resin of embodiment 1 | 53.4 | 53.3 | 33.0 | |||||
| The dihydroxyphenyl propane diglycidyl ether of EEW=180.4, Mn=422, Mw/Mn=1.1 | 50.3 | |||||||
| Hydroxyl equivalent is the solid phenol aldehyde type stiffening agent of 240-270 | 15.8 | 21.7 | 17.9 | 16.8 | 18.7 | |||
| MODAFLOW (2) | 0.4 | 0.4 | 0.5 | 0.45 | 0.5 | |||
| Flowing agent (Resi Flow PV5) (3) | 1.0 | 1.0 | 1.0 |
Table I (continuing)
| Component (weight part) | ??2 * | ??3 | ??4 | ??5 * | ??6 * | ??7 | ??8 | ????9 |
| 1,3-phenoxy group-2-propyl alcohol 98% methyl iso-butyl ketone (MIBK) 2% | ??1.0 | ??1.0 | ??1.0 | |||||
| TiO 2(KRONOS?2310) (4) | ??25.0 | ??25.0 | ??25.0 | ??25.0 | ??28.0 | ??28.0 | ??28.0 | ????25 |
| BaSO 4 (7) | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ????5.0 | |||
| Glyoxal ethyline | ??0.45 | ??0.45 | ??0.54 | ??0.5 | ????0.54 | |||
| 180 ℃ of gelation times of observations (second) (storing after 42 days) mobility status (is divided into the 1-4 level, the 1=uniform coating; 4=plays tangerine peel) | ??45 ??(1) | ??45 ??1 | ??49 ??(35) ??2 | ??47 ??(43) ??(1) | ??107 | ??293 | ??190 | ????35 |
| Shock strength (8)The cm.kg steel plate (5)Just/115 ℃ 120 ℃ of 110 ℃ of solidification values of reverse side | ??(5) ??184/ ??184 ??184/ ??184 ??184/ ??184 | ??(5) ??115/ ??34.5 ??184/5 ??7.5 ??184/5 ??7.5 | ??(5) ??34.5/ ??34.5 ??184/ ??161 | ??(5) ??34.5/ ??34.5 ??184/ ??184 | 15 minutes 184/ 184 | |||
| Impression (9)Mm, steel plate (5)With (6)140 ℃ of solidification temperatures-5 of 120 ℃ of solidification temperatures of 115 ℃ of solidification temperatures of 110 ℃ of solidification temperatures minutes-20 minutes-22.5 minutes | ??(5) ??8.8 ??8.3 ??8.2 | ??(5) ??8.6 ??8.2 ??8.6 | ??(5) ??0.5 ??8.7 | ??(5) ??0.5 ??8.5 | ??(6) ??7.4 ??7.5 ??7.4 | ??(6) ??0.5 ??0.5 ??0.5 | ??(6) ??0.5 ??1.0 ??7.4 |
*Embodiments of the invention
(1) Uralac P 2980, and German DSM Kunstharze company provides Am Kreisforst 1, D-49716 Meppen, Germany
(2) MODAFLOW
TMThe polyacrylate(s) flow ability modifying agent, Monsanto EuropeSA provides, Brussels, BELGIUM
(3) ResiFlow PV5 polyacrylate(s) flow ability modifying agent, Worlee Chem. provides, Lauenburg/Elbe, Germany
(4) KRONOS 2310 titanium dioxide, Kronos Titan company provides LeverkusenGermany
(5) DIN 1624-ST4 steel, degrease 1mm is thick
(6) Bonder
TM1041600C, chromate treating, clean usefulness, 1mm is thick.Bonder is the Chemetall trade mark, Frankfurt/Main, Germany
(7)EWO，Sachleben?Chemie，Duisberg，GERMANY
(8) 614,20 minute set time of ASTM, except as otherwise noted
(9) 53156,20 minute set time of DIN, except as otherwise noted
Table II
| Embodiment 10 (weight part) | Embodiment 11 *(weight part) | |
| The dihydroxyphenyl propane diglycidyl ether | ????67.9 | ????22.36 |
| Dihydroxyphenyl propane | ????32.1 | ????10.33 |
| Acetate Yi base triphenyl phosphonium | ????0.05 | ????0.0207 |
| Methyl tosylate | ????- | ????0.008parts |
| Epoxy equivalent (weight) | ????520 | ????438 |
| Epoxide % (weight) | ????8.25 | ????9.82 |
| Molecular weight (Mn) | ????1398 | ????925 |
| Molecular weight (Mw) | ????4331 | ????2000 |
| Mw/Mn | ????3.1 | ????2.2 |
| The epoxy functional degree is 3.6, Mn is 534, the epoxidization phenolic resin of Mw/Mn=1.7 | ????22.9 ????(18.6％) | ????7.5 ????(18.7％) |
Embodiment 12-17
Embodiment 12-17 has the character of the composition epoxy resin of identical epoxy group(ing)/phenolic hydroxyl group ratio to compare in raw material.All compositions all are blended in Mixaco container mixing machine, then at 63 ℃ in Werner ﹠amp; Melt extrude in Pfleiderer ZSK 30 extrusion machines.After extruding and cooling off, solid resin is ground to form size be that the sample of 1-100 μ m, its average particle size distribution are 25-40 μ m.
Table III is composition and the coating property of embodiment 11-16.
Embodiment 18
The mixture and mixed being incorporated in of 316 parts of dihydroxyphenyl propanes (2.77 equivalent) of 584 parts of dihydroxyphenyl propane diglycidyl ether (EEW 178,3.28 equivalents) are heated with stirring to 95 ℃ in the nitrogen atmosphere.Add 0.21 part of acetate Yi base triphenyl phosphonium solution then as prepolymerization catalyst/initiator.Carefully temperature is risen to 125 ℃ and to keep this temperature be 5Pas (measuring at 120 ℃ of cone-and-plate viscometer with ICI) until the value of the melt viscosity of resin.Add methyl tosylate (0.8 part), then add 100 parts of epoxy functional degree and be 3.6, Mn is 534, Mw/Mn is 1.7 epoxidization phenolic resin.The weight percentage of the epoxy group content of the Resins, epoxy that obtains is 5-12%, epoxide equivalent weight is 350-900, the Mettler softening temperature is 70-100 ℃, melt viscosity is for being lower than 1.0Pas (150 ℃), 1-5Pas (120 ℃) and 5-40Pas (100 ℃), the number-average molecular weight scope is 750-1500 (Mn), polydispersity index is 1.25-5.0, and second-order transition temperature (Tg) is greater than 30 ℃.This resin can be 90-180 ℃ of curing as coating, and set time is in 30-10 minute.
Embodiment 19
Except that 484 parts of dihydroxyphenyl propane diglycidyl ether with 200 parts of epoxy functional degree be 3.6, Mn is 534, Mw/Mn 1.7 epoxidization phenolic resin uses, can prepare another resin by embodiment 17.Identical among other amount and condition and the embodiment 1.
Table III
| ????12 | ???13 | ????14 | ????15 | ???16 * | ????17 | |
| Fs component dihydroxyphenyl propane dihydroxyphenyl propane diglycidyl ether | ?11.93 ?37.80 | ??17.80 ??39.63 | ??14.33 ??38.75 | ??13.33 ??28.39 | ??13.33 ??28.39 | ??11.90 ??37.72 |
| The subordinate phase component | ??9.5 | ??9.5 | ||||
| The Tg of subordinate phase resin (℃) | ?29.3 | ??54.0 | ??46.1 | ??46.0 | ??34.0 | ??- |
| The formulation for coating material hydroxyl equivalent that stiffening agent is arranged is the solid phenol aldehyde type stiffening agent of 240-270 | ?19.82 | ??12.14 | ??16.47 | ??18.30 | ??18.18 | ??19.77 |
| Glyoxal ethyline | ?0.45 | ??0.45 | ??0.45 | ??0.45 | ??0.45 | ??0.6 |
| TiO 2(Kronos?2310) | ?29 | ??29 | ??29 | ??29 | ??29 | ??29 |
| MODAFLOW TM?III | ?1 | ??1 | ??1 | ??1 | ??1 | ??1 |
| Total weight parts | ?100 | ??99.72 | ??100 | ??99.97 | ??99.85 | ??99.84 |
| 180 ℃ of gelation times (second) | ?63.5 | ??69.0 | ??67.5 | ??47.5 | ??45.0 | ??52.0 |
| Coating property (1) | ||||||
| Coat-thickness/flow assessment (2)115 ℃ 120 ℃ of 110 ℃ of solidification values (25 minutes) | ?73/4.6 ?86/4.6 ?88/4.1 | ??77/1.9 ??89/1.7 ??80/1.8 | ??75/2.1 ??69/2.0 ??73/2.7 | ??82/2.3 ??87/2.3 ??80/1.7 | ??63/2.7 ??72/3.8 ??76/4.3 | ??87/4.2 ??96/4.7 ??92/4.9 |
| Shock test cmkg P=is qualified, 120 ℃ of 110 ℃ of 115 ℃ of 25 minutes solidification values of the defective front/reverse side of f= | ?f23/f23 ?p57.5/ ?f23 ?p184/ ?p184 | ??f23/f23 ??p184/ ??p184 ??p184/ ??p184 | ??f23/f23 ??p184/ ??p184 ??p184/ ??p184 | ??f23/f23 ??p57.5/ ??f23 ??p184/ ??p184 | ??f23/f23 ??p184/ ??p184 ??p184/ ??p184 | ??f23/f23 ??p184/ ??p184 ??p184/ ??p184 |
| 115 ℃ 120 ℃ of 25 minutes temperature of 110 ℃ of curing of impression mm | ?0.5 ?9.5 ?9.5 | ??0.5 ??10.0 ??10.0 | ??9.5 ??10.0 ??10.0 | ??2.3 ??9.5 ??9.5 | ??1.0 ??9.4 ??9.3 | ??8.2 ??8.5 ??9.5 |
(1) steel is DIN 1624-ST4, and degrease 1mm is thick
(2) flow assessment is measured the ByK-Gardnerwave-scan mensuration of carrying out according to operation instructions handbook (1992).ByK-gardener?Gmbh，D-82538?Geretsried，Germany。Evaluation is divided into 0 (very poor)-10 (fabulous) level
(3) the epoxy functional degree be 3.6, the epoxidization phenolic resin of Mn 534
Embodiment 20-24
Meshing co-rotating twin screw extruder, with 100 rev/mins rotary speed working with reactive ZSK-30.The long 1410mm of machine barrel does not comprise die head.Machine barrel comprises 11 single length (900mm) and two two length (180mm) barrel section and the supporting plate of a 30mm is arranged and the end plate of a 30mm.Barrel configuration has a feeding part, then is solid part, vent portion, and the rest part of machine barrel is alternative plunger part and solid part.Extruder head has stress measuring device, broken material disk and pump and takes out interface.4 thorough mixing portions are arranged in screw design, stretch in the extruder head.Machine barrel is divided into 9 heating and cooling districts.The 9th zone is extruder head.Under feeding rate shown in the Table IV by feedstock production Resins, epoxy.The 1-3 district is 175 ℃ of operations, and the 4th district is 220 ℃ of operations, and the 5th and 6 districts are 240 ℃ of operations, and the 7-9 district is 175 ℃ of operations.
Table IV
| Embodiment | ????20 | ????21 | ????22 * | ????23 * | ????24 * |
| EEW is 1804, the dihydroxyphenyl propane diglycidyl ether of Mn=422, Mw/Mn=1.1 | ?5.05kg/h | ?5.1kg/h | ?5.1kg/h | ?5.1kg/h | ?5.1kg/h |
| The epoxy functional degree is 3.6, Mn is 534, the epoxidization phenolic resin of Mw/Mn=1.7, EEW=177 | ?1.7kg/h | ?1.7kg/h | ?1.7kg/h | ||
| Dihydroxyphenyl propane | ?2.3kg/h | ?2.3kg/h | ?2.3kg/h | ?2.3kg/h | ?2.3kg/h |
| Acetate Yi base triphenyl phosphonium | ?300ppm | ?300ppm | ?300ppm | ?300ppm | ?300ppm |
| The subordinate phase resin properties: |
| Epoxide equivalent weight phenol equivalent weight | ??661 ??10800 | ????661 ????9139 | ????440 ????7217 | ????442 ????6704 | ??441 ??7321 |
| Molecular weight: Mn Mw | ??N.A. | ????N.A. | ????N.A. | ????N.A. | ??693 ??1914 |
*Embodiments of the invention
Claims
Stop according to the ester of the acid anhydride of the modification of the 19th of treaty or strong acid.
16. the method for claim 7, wherein strong acid, acid anhydride or ester are phosphoric acid, phosphoric anhydride, and methyl-sulfate is such as alkyl and aryl sulfonic acid, trichoroacetic acid(TCA), methyl tosylate, ethyl p-toluenesulfonate and the methyl mesylate of tosic acid.
17. the method for claim 7, wherein epoxy group(ing)-hydroxyl reaction is to stop to being enough to the method for temperature-control by that effective stopped reaction carries out to being enough to destroy catalysts or cooling reactant by increase temperature in forcing machine.
18. one kind is to solidify the thermosetting epoxy resin coating that obtains in 30-10 minute 90 ℃-180 ℃ and set time, it have when being applied on DIN 1624 steel plates shock strength greater than 115cmkg (front), greater than 34.5cmkg (reverse side), Erichsen impression greater than 6mm, Byk flowability greater than 2.
19. the thermosetting epoxy resin coating of claim 18, it solidifies in 30-10 minute set time in 90-120 ℃.
Claims (19)
1. the Resins, epoxy that comprises polyepoxide and polyol reaction product, wherein this reaction product comprises epoxy group(ing) and end phenolic hydroxyl group, and its amount respectively is at least about 0.2% (weight), and said weight percentage is based on Resins, epoxy reaction product total weight; Improvement wherein comprises and adds the epoxy functional degree greater than 2 epoxidization phenolic resin.
2. the Resins, epoxy of claim 1, wherein polyol reactant is the polyol reactant of formula I
In the formula, A is independently of one another-S-,-S-S-,-C (O)-,-S (O)-,-S (O)
2-, contain the bivalent hydrocarbon radical of 1-8 carbon atom or contain the alkyl or a covalent linkage of oxygen, sulphur or nitrogen, A also can be
X is hydrogen, halogen or the alkyl that contains 1-4 carbon atom independently of one another, mean value＞0-5 of n, preferred 0-2; Or the polyol reactant of formula II
In the formula, respectively do for oneself hydrogen or the alkyl of 1-4 carbon atom is arranged of R, Y are independently of one another for hydrogen, chlorine, bromine or the low alkyl group of 1-4 carbon atom is arranged, and the mean value of m is greater than 0 to 10; Or the composition mixture of formula I and II;
And the epoxy reaction thing is the reactant of formula III
In the formula, described in each A and X such as the preceding formula I, the mean value of n is 0-4, or the reactant of formula IV
In the formula, described in R, Y and m such as the following formula II, or many glycidyl ethers (such as polypropylene glycol diglycidyl ether) of polyglycol or the many glycidyl ethers of three (phenol) methane or triazine triglycidyl group ether (for example triglycidyl isocyanurate) or their mixture, the epoxy group(ing) component is 0.1 with the hydroxy component ratio: 1-10: 1; The catalysts of inhibited reaction process has at least about the terminal hydroxy group of 0.2% (weight) with at least about the end epoxy group(ing) of 0.2% (weight) when predetermined reaction conversion ratio resin.
3. the Resins, epoxy of claim 2, the n mean value of its Chinese style I component is 0-2.
4. the Resins, epoxy of claim 2, the m mean value of its Chinese style II component is 0-4.5.
5. the Resins, epoxy of claim 2, wherein the n mean value of formula III component is 0-2.
6. the Resins, epoxy of claim 2, the m mean value of reactant/component of its Chinese style IV is 0.5-4.5.
7. method for preparing Resins, epoxy, this method are included under the isothermal condition polyol reactant with formula I
In the formula, A is independently of one another-S-,-S-S-,-C (O)-,-S (O)-,-S (O)
2-, contain the bivalent hydrocarbon radical of 1-8 carbon atom or contain the alkyl or a covalent linkage of oxygen, sulphur or nitrogen, A also can be
X is hydrogen, halogen or the alkyl that contains 1-4 carbon atom independently of one another, and the mean value of n is 0-5, preferred 0-2; Or the polyol reactant of formula II
In the formula, respectively do for oneself hydrogen or the alkyl of 1-4 carbon atom is arranged of R, Y is independently of one another for hydrogen, chlorine, bromine or the low alkyl group of 1-4 carbon atom is arranged, and the mean value of m is greater than 0 to 10 or the composition mixture of formula I and formula II and the epoxy reaction thing III of formula III
In the formula described in each A and X such as the preceding formula I, the mean value of n be 0-4 or with the epoxy reaction thing of formula IV
In the formula described in R, Y and m such as the following formula II, or many glycidyl ethers (such as polypropylene glycol diglycidyl ether) of polyglycol or the many glycidyl ethers of three (phenol) methane or triazine triglycidyl group ether (for example triglycidyl isocyanurate) or the mixing of its mixture, making epoxy group(ing) component and hydroxy component ratio is 0.1: 1-10: 1, also comprise the catalysts that an inhibited reaction carries out, when predetermined reaction conversion ratio resin is had at least about the terminal hydroxy group of 0.2% (weight) with at least about the end epoxy group(ing) of 0.2% (weight).
8. the method for claim 7, the n mean value of its Chinese style I component is 0-2.
9. the method for claim 7, the m mean value of its Chinese style II component is 0.5-4.5.
10. the method for claim 7, wherein the n mean value of formula III component is 0-2.
11. the method for claim 7, the m mean value of its Chinese style IV reactant is 0.5-4.5.
12. the method for claim 7, wherein the mol ratio of epoxy group(ing) component and phenolic hydroxyl group component is 0.3: 1-5: 1.
13. the method for claim 7, wherein the reaction of hydroxy component and epoxy group(ing) component is by following catalyst: the tertiary amine or the secondary amine that are selected from benzyldimethylamine, triethylamine and/or benzyl diethylamine, alkali metal hydroxide such as potassium hydroxide are such as quaternary ammonium compound and/or phosphine compound and/or quaternary alkylphosphonium salt such as the triphenyl phosphine and/or the acetate Yi base San Ben Phosphonium of halogenation tetra-allkylammonium (for example tetramethylammonium chloride).
14. the method for claim 7, wherein reaction mixture remains under the isothermal condition.
15. the method for claim 7, wherein epoxy group(ing)-hydroxyl reaction is to stop by the acid anhydride of adding strong acid, strong acid or the ester of strong acid.
16. the method for claim 7, wherein strong acid, acid anhydride or ester are phosphoric acid, phosphoric anhydride, and methyl-sulfate is such as alkyl and aryl sulfonic acid, trichoroacetic acid(TCA), methyl tosylate, ethyl p-toluenesulfonate and the methyl mesylate of tosic acid.
17. the method for claim 7, wherein epoxy group(ing)-hydroxyl reaction is to stop to being enough to the method for temperature-control by that effective stopped reaction carries out to being enough to destroy catalysts or cooling reactant by increase temperature in forcing machine.
18. one kind is to solidify the thermosetting epoxy resin coating that obtains in 30-10 minute 90 ℃-180 ℃ and set time, it have when being applied on the steel plate shock strength greater than 115cmkg (front), greater than 34.5cmkg (reverse side), Erichsen impression greater than 6mm, Byk flowability greater than 2.
19. the thermosetting epoxy resin coating of claim 18, it solidifies in 30-10 minute set time in 90-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95197587 CN1175265A (en) | 1995-02-10 | 1995-02-10 | Epoxy resin composition capable of cure at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95197587 CN1175265A (en) | 1995-02-10 | 1995-02-10 | Epoxy resin composition capable of cure at low temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1175265A true CN1175265A (en) | 1998-03-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95197587 Pending CN1175265A (en) | 1995-02-10 | 1995-02-10 | Epoxy resin composition capable of cure at low temperature |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347250C (en) * | 2005-10-10 | 2007-11-07 | 湘潭市至诚涂料有限公司 | Cryogenic curing powdery coating for heat-sensitive substrate material |
| CN101784624B (en) * | 2007-08-23 | 2013-09-25 | 日本油漆株式会社 | Powder coating composition for PC strand coating, coating method, and coating film |
| CN104364287A (en) * | 2012-06-15 | 2015-02-18 | 陶氏环球技术有限责任公司 | Latent catalyst for curable compositions |
| CN109627427A (en) * | 2018-11-19 | 2019-04-16 | 天津翔盛新材料有限公司 | A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints |
| CN111944422A (en) * | 2020-08-24 | 2020-11-17 | 湖北武洲新材料科技有限公司 | Low-temperature fast-curing high-temperature-resistant non-oriented electrical steel environment-friendly C6-grade insulating paint |
| CN114585661A (en) * | 2019-11-29 | 2022-06-03 | 国都化学株式会社 | Method for preparing ultra-low temperature fast curing epoxy resin and composition for powder coating containing resin prepared thereby |
-
1995
- 1995-02-10 CN CN 95197587 patent/CN1175265A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347250C (en) * | 2005-10-10 | 2007-11-07 | 湘潭市至诚涂料有限公司 | Cryogenic curing powdery coating for heat-sensitive substrate material |
| CN101784624B (en) * | 2007-08-23 | 2013-09-25 | 日本油漆株式会社 | Powder coating composition for PC strand coating, coating method, and coating film |
| CN104364287A (en) * | 2012-06-15 | 2015-02-18 | 陶氏环球技术有限责任公司 | Latent catalyst for curable compositions |
| CN109627427A (en) * | 2018-11-19 | 2019-04-16 | 天津翔盛新材料有限公司 | A kind of preparation method of low viscosity epoxy resin and super levelling powdery paints |
| CN114585661A (en) * | 2019-11-29 | 2022-06-03 | 国都化学株式会社 | Method for preparing ultra-low temperature fast curing epoxy resin and composition for powder coating containing resin prepared thereby |
| CN111944422A (en) * | 2020-08-24 | 2020-11-17 | 湖北武洲新材料科技有限公司 | Low-temperature fast-curing high-temperature-resistant non-oriented electrical steel environment-friendly C6-grade insulating paint |
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