CN101591424B - Fast epoxy resin curing agent and preparation method thereof - Google Patents
Fast epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN101591424B CN101591424B CN2008100380382A CN200810038038A CN101591424B CN 101591424 B CN101591424 B CN 101591424B CN 2008100380382 A CN2008100380382 A CN 2008100380382A CN 200810038038 A CN200810038038 A CN 200810038038A CN 101591424 B CN101591424 B CN 101591424B
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Abstract
The invention discloses a fast epoxy resin curing agent and a preparation method thereof. The preparation method comprises the following steps: (1) hydroxyl compound and phosphoric acid esterifying reagent polyphosphoric acid react under the protection of an inert gas, the hydroxyl transformation rate is controlled to be higher than 95 percent, and then water accounting for 1-5 percent of the weight of the phosphoric acid esterifying reagent is added for hydrolysis, therefore, the content of phosphate mono-ester is caused to be over 60 percent, the content of phosphate di-ester is caused to be no higher than 30 percent, and the content of free phosphoric acid is caused to be no higher than 10 percent; and (2) a metal ion compound is added for reaction and then the product can be obtained. The curing agent obtained according to the preparation method, has the excellent properties of light color, high gloss, difficult oxidization, no yellowing, good weather resistance, and the like after being subjected to curing reaction with epoxy resin. Meanwhile, the curing agent of such type has the advantages of low toxicity, low volatility, low odor and low acrimony, and the color is light and conforms to the requirement of present environmental-friendly development.
Description
Technical field
The present invention relates to a kind of solidifying agent, particularly relate to a kind of ion complexation type phosphoric acid ester solidifying agent that is used for Resins, epoxy.
Background technology
Resins, epoxy is the very important industrial chemicals of a class, usually adding a certain proportion of solidifying agent, mix the back and solidify under the condition of normal temperature or heating, it has excellent mechanical intensity, erosion resistance, electrical insulating property to be widely used in coating, tackiness agent, plastics, prepare composite after solidifying.Can make the material of Resins, epoxy resin solidification a lot, a lot of occasions need be cured bonding under the condition of room temperature, this just needs to use active higher self-vulcanizing agent, low molecule amine such as diethyl triamine, triethyl tetramine etc. are effective cured epoxy resin at normal temperatures, is common self-vulcanizing agent.But low molecular amine solidifying agent has smell and toxicity is big, shortcomings such as easy oxidation xanthochromia.For this reason, there are a lot of new technologies and method to carry out modification, obtain a kind of self-vulcanizing agent that reached intensity in 30 minutes by modified polyamine, oxy-compound and thiocarbamide mixture as Chinese patent 200410022810; The open CN1289348 of Chinese patent discloses a kind of mercaptan compound that can room temperature reacts with Resins, epoxy; The CAPCURE of Henkel Corp.
3830-81 also is the sulfur alcohol compound of a class tertiary amine catalytic, and it has curing activity preferably at low temperature, and color is also lower, has not limited its large-area application but its unique stink and cured product physical strength thereof are high.
On the other hand, polymkeric substance fire-retardant very important in application proved that the compound of phosphorus element-containing possesses flame retardant resistance, has been widely used in the every field of industry as fire retardant as the phosphoric acid ester material.Phosphoric is introduced curing agent for epoxy resin, to possess flame retardant resistance be highly effective and give cured product simultaneously, as Chinese patent CN1681865, United States Patent (USP) 4973631,6403220 and Japanese Patent JP61134395, they all adopted have can and the phosphorus oxide compounds of replacements such as the group of Resins, epoxy reaction such as amido, sulfydryl, phenolic hydroxyl group.Chinese patent CN101050331 relates to a kind of phosphate ester acid and epoxy resin cure as fire-retardant fireproof coating.Contriver's patent PCT/CN2004/000034 in early stage utilizes polyphosphoric acid and hydroxy-containing compounds prepared in reaction phosphate ester acid, can with the epoxy resin at room temp fast setting, but still have the not good defective of resistance to medium, influence use range and performance.
Summary of the invention
The purpose of this invention is to provide a kind of fast epoxy resin curing agent and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Fast curable epoxy solidifying agent provided by the present invention, its general structure are suc as formula (1):
Wherein: R
1And R
2Be H or other organic substituent group, R
1And R
2Can be identical or different;
Work as R
1Or R
2Be hydrogen, be expressed as the mono-esterification phosphoric acid ester;
Work as R
1And R
2All be substituted expression double esterification phosphate compound;
M is a metal ion, and preferred L is that metal ion is the metal ion that Zn, Ca, Fe or Cu etc. have the multivalence state;
Other organic substituent group comprises alkyl, alkoxyl group or ester group;
On molecular structure, can contain single phosphoric acid functional group on the individual molecule, also can be two, or even a plurality of;
Simultaneously, metal ions M is at least one, also can be two or more;
In the same molecular structure, has a phosphoric acid functional group at least.
The preparation method of above-mentioned compound comprises the steps:
(1) with oxy-compound and Phosphation reagent polyphosphoric acid, under protection of inert gas, react, temperature of reaction is 50～150 ℃, be preferably 60～110 ℃, reaction times is 2～8 hours, according to system viscosity, can add organic solvent, the transformation efficiency of control hydroxyl is greater than 95%, and the water that adds the 1-5% of Phosphation reagent weight then is hydrolyzed, and hydrolysis temperature is normal temperature～100 ℃, time is 1～5 hour, make phosphate monoester content greater than 60%, the content of phosphate diester is not higher than 30%, and free phosphoric acid is not higher than 10%;
Calculate with Vanadium Pentoxide in FLAKES, Phosphation reagent: oxy-compound is 1: 2-6, mol ratio;
Described Phosphation reagent is polyphosphoric acid or Vanadium Pentoxide in FLAKES;
Described organic solvent is selected from the common solvent such as fat alkane, aromatic hydrocarbon, ketone, ester class, alcohols, and system viscosity is controlled at and is suitable for stirring.
(2) add metal ion compound, in the P-OH of phosphate ester acid, the add-on of metal ion is that the molecular fraction of P-OH is 10～50%, and temperature of reaction is 20～65 ℃, and the reaction times is 2～10 hours, can obtain product;
The selection of described oxy-compound is a lot, all compounds that can carry out the hydroxyl of phosphinylidyne esterification can both be prepared into the phosphorated epoxy curing agent in principle, can be the micromolecular hydroxyl compound that definite molecular structure is arranged, as monohydroxy-alcohol: methyl alcohol, ethanol, Virahol, butanols, lauryl alcohol, 16 pure, stearyl alcohol, phenylcarbinol, hydroxyethyl methylacrylate and phenol etc.; Dibasic alcohol: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, hexylene glycol, Diethylene Glycol and dihydroxyphenyl propane etc.; Polyvalent alcohol: glycerol, tetramethylolmethane, glucose etc.The polyether glycol that also can possess the polymer hydroxy-containing compounds of certain molecular weight such as different molecular weight, different functionality, different structure: polyoxyethylene glycol, polypropylene glycol, polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene-castor oil polyhydric alcohol and polytetrahydrofuran diol etc.; Polyester polyol: polyethylene glycol adipate glycol, poly-hexanodioic acid Diethylene Glycol esterdiol, poly adipate succinic acid ester glycol, polycaprolactone glycol and poly-carbonic acid 1,6-hexylene glycol esterdiol etc.; Polybutadiene diol; The butadiene-acrylonitrile copolymer glycol; Hydroxylated acrylic resin; The organic hydroxy silicate resin; Hydroxyl organic fluorine etc.
Described metal ion is a multiselect, can with the phosphate radical reacting generating complex, be preferably calcium metal, chromium, iron, copper, zinc or magnesium.
Solidifying agent provided by the present invention is complexing of metal ion phosphorous epoxy resin solidifying agent, compares with existing amine or thio-alcohol normal temperature epoxy resin curing agent or phosphate ester acid solidifying agent, and following advantage is arranged:
1. along with the difference of molecular structure, by regulating the variation of phosphate group equivalent and complexation of metal ions, can adjust curing speed, 25 ℃ down the initial gel time of the mixture of the Resins, epoxy of 50 grams and solidifying agent can several minutes or the dozens of minutes sclerosis reach suitable physical strength solidify construction under the different occasion conditions so that be suitable for.
2. according to curing mechanism; phosphate ester acid contain can with the P-OH of epoxy-functional reaction; because curing speed is very fast; usually can cause reaction not exclusively; free P-OH can promote the destroying infection performance of resin; because the metal ion of complexing is arranged in the system, can with the P-O coordination, have splendid resistance to medium behind the curing reaction.
3. behind the curing reaction of this solidifying agent and Resins, epoxy, having a look shallow, and high gloss is difficult for oxidation, not yellowing, excellent properties such as good weatherability.Such solidifying agent possesses hypotoxicity, low volatility, low smell, low irritant, the look shallow demand for development that meets present environmental protection simultaneously.
Embodiment
Come furthermore bright the present invention below by embodiment, but do not limit the scope of the present invention, all are that the present invention is claimed based on the modification and the change of basic thought of the present invention.
The raw material of selecting for use in following examples is:
Resins, epoxy: epoxy equivalent (weight) is 190, as 828 of Shell Co. Ltd
Polyphosphoric acid: 80% phosphorus pentoxide content
The mensuration of set time: rise to the time that to stir from beginning to be mixed to viscosity with Resins, epoxy and solidifying agent
The mensuration of bonding strength: with reference to ASTM D1002.
Embodiment 1
Adding 740 gram molecular weights in 2 reactors of stirring, thermometer and Dropping feeder are housed is 400; hydroxy radical content is 5mmol/g; the linear polyoxypropyleneglycol of two functionality (polyethers 204); drip 177.5 gram polyphosphoric acid while stirring, and logical argon shield, about 80 ℃ of control reaction temperature; after dropwising; attemperation is at 60 ℃ and be incubated logical argon gas reaction 2 hours, and then adds 3 gram water, continues insulation reaction 2 hours.Cooling adds 50 gram Zn (CH at 30 ℃
3COO)
2, stirring reaction 2 hours obtains faint yellow thickness transparent liquid.
After Resins, epoxy 828 mixed with mass ratio at 40: 100, the mixture of 50 grams was 25 ℃ of curing in following 15 minutes.Cured article is immersed in 25 ℃ the water, increases weight 1% after 30 days, smooth surface is defined as this and has excellent water-resistance.
The comparative example:
With above-mentioned preparation process, just do not add Zn (CH after the esterification
3COO)
2, still with after Resins, epoxy 828 mixes with mass ratio at 40: 100, the mixtures of 50 grams solidified at 25 ℃ in following 15 minutes, as seen the curing speed of the two is consistent.But cured article is immersed in 25 ℃ the water, after 10 days, increases weight and increase weight 50% after 16%, 30 day, it is relatively poor that this can only be defined as water tolerance.
Embodiment 2
In being housed, 1 liter of reactor of stirring, thermometer and Dropping feeder adds 177.5 gram polyphosphoric acid; drip 76 gram propylene glycol while stirring; and logical argon shield, control reaction temperature is lower than 80 ℃, after dropwising; be warming up to 80 ℃ and also be incubated logical argon gas reaction 3 hours. and then add 5 gram water; continue insulation reaction 2 hours, and be cooled to 60 ℃, add calcium naphthenate 7 grams; continued stirring reaction 2 hours, cooling obtains obtaining the light brown transparent liquid.
After Resins, epoxy 828 mixed with mass ratio at 24: 100, the mixture of 50 grams was 25 ℃ of curing in following 2 minutes.Cured article is immersed in 25 ℃ 5% the NaOH aqueous solution, increases weight 1.5% after 7 days, smooth surface, it is good that this is defined as alkaline-resisting water-based.
The comparative example:
With above-mentioned preparation process, just do not add calcium naphthenate after the esterification, still with after Resins, epoxy 828 mixes with mass ratio at 24: 100, the mixtures of 50 grams solidified at 25 ℃ in following 2 minutes, as seen the curing speed of the two is a unanimity.But cured article is immersed in 5% the NaOH aqueous solution, after 7 days, cured article is hydrolysis substantially, and it is poor that this can only be defined as alkali resistance.
Embodiment 3
For verifying the performance of this solidifying agent and epoxy resin cure, the solidifying agent that embodiment 1 is obtained is with after Resins, epoxy 828 mixes with mass ratio at 40: 100, be used for stainless steel/stainless bonding, 25 ℃ place 24 hours after, its average tensile shear strength is respectively 25MPa.
Claims (1)
1. prepare the method for fast epoxy resin curing agent, it is characterized in that, comprise the steps:
(1) with oxy-compound and Phosphation reagent polyphosphoric acid, under protection of inert gas, react, the transformation efficiency of control hydroxyl is greater than 95%, the water that adds the 1-5% of Phosphation reagent weight then is hydrolyzed, make phosphate monoester content greater than 60%, the content of phosphate diester is not higher than 30%, and free phosphoric acid is not higher than 10%; Described oxy-compound is methyl alcohol, ethanol, butanols, propylene glycol, butyleneglycol, glycerol, tetramethylolmethane, polyether glycol, polyester polyol, polybutadiene diol or butadiene-acrylonitrile copolymer glycol;
(2) add metal ion compound, temperature of reaction is 20～65 ℃, and the reaction times is 2～12 hours, can obtain the fast epoxy resin curing agent of formula (1), and described metal ion is selected from calcium metal, chromium, iron, copper, zinc or magnesium;
Wherein: R
1And R
2Be H, alkyl, alkoxyl group or ester group, R
1And R
2Can be identical or different;
M is a metal ion; On molecular structural formula (1), metal ions M is at least one;
The temperature of reaction of step (1) is 60～150 ℃, and the reaction times is 2～8 hours;
Calculate with Vanadium Pentoxide in FLAKES, Phosphation reagent: oxy-compound is 1: 2-6, mol ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100380382A CN101591424B (en) | 2008-05-26 | 2008-05-26 | Fast epoxy resin curing agent and preparation method thereof |
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|---|---|---|---|
| CN2008100380382A CN101591424B (en) | 2008-05-26 | 2008-05-26 | Fast epoxy resin curing agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101591424A CN101591424A (en) | 2009-12-02 |
| CN101591424B true CN101591424B (en) | 2011-11-23 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086262B (en) * | 2010-11-10 | 2012-12-26 | 张家港卡邦新材料有限公司 | Epoxy resin flexibilizer as well as preparation method and application thereof |
| CN107383993A (en) * | 2017-07-19 | 2017-11-24 | 东莞市左镕工实业有限公司 | Phosphide type auxiliary agent for elastic handfeel paint and preparation method thereof |
| CN107629195B (en) * | 2017-11-03 | 2020-01-10 | 昆明迈泽科技有限公司 | Preparation method and application of phosphate modified cashew nut oil curing agent |
| CN112851925B (en) * | 2021-02-02 | 2023-01-31 | 扬州晨化新材料股份有限公司 | Preparation method of mixed phosphorus-containing polyol flame retardant |
| CN113502597B (en) * | 2021-06-28 | 2022-09-16 | 南通大学 | Flexible high-infrared-reflectivity yttrium manganate nanofiber membrane and preparation method thereof |
| CN114031895B (en) * | 2021-11-15 | 2022-07-05 | 浙江豪德盛绝缘材料有限公司 | Preparation method of high-corrosion-resistance epoxy resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973631A (en) * | 1989-10-06 | 1990-11-27 | Virginia Tech Intellectual Properties Inc. | Novel phosphorus containing epoxy networks |
| CN1916049A (en) * | 2006-08-18 | 2007-02-21 | 中国科学院广州化学研究所 | Epoxy resin curing agent of containing phosphor, prepartion method and applicaiton |
| CN101050331A (en) * | 2007-05-15 | 2007-10-10 | 河北大学 | Room temperature solidified expansion type flame-resistant fire retardant coating of epoxy resin, and preparation method |
-
2008
- 2008-05-26 CN CN2008100380382A patent/CN101591424B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973631A (en) * | 1989-10-06 | 1990-11-27 | Virginia Tech Intellectual Properties Inc. | Novel phosphorus containing epoxy networks |
| CN1916049A (en) * | 2006-08-18 | 2007-02-21 | 中国科学院广州化学研究所 | Epoxy resin curing agent of containing phosphor, prepartion method and applicaiton |
| CN101050331A (en) * | 2007-05-15 | 2007-10-10 | 河北大学 | Room temperature solidified expansion type flame-resistant fire retardant coating of epoxy resin, and preparation method |
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