CN102286137A - Preparation method of polyether modified epoxy resins used for marine concrete paint - Google Patents
Preparation method of polyether modified epoxy resins used for marine concrete paint Download PDFInfo
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- CN102286137A CN102286137A CN2011101245106A CN201110124510A CN102286137A CN 102286137 A CN102286137 A CN 102286137A CN 2011101245106 A CN2011101245106 A CN 2011101245106A CN 201110124510 A CN201110124510 A CN 201110124510A CN 102286137 A CN102286137 A CN 102286137A
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Abstract
The invention relates to a preparation method of polyether modified epoxy resins used for the marine concrete paint, belonging to the synthesis field of the organic chemical material. The preparation method comprises the following specific steps: using epoxy resins and acrylic acid to perform a ring opening reaction and prepare epoxy acrylic resins; using diisocyanate and polyether to perform an addition reaction and prepare an isocyanate-terminated prepolymer; and finally using the isocyanate-terminated prepolymer and epoxy acrylic resins to perform a crosslinking reaction and prepare an interpenetrating network polymer, namely polyether modified epoxy resins. The modified epoxy resins have higher flexibility; and the resins are cured to form a dense film with good toughness and the impact resistance is better, thus the corrosion resistance of the resins can be increased.
Description
Technical field
The invention belongs to the synthetic field of organic materials, be specifically related to a kind of preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating, be characterized in forming a kind of while inierpeneirating network structure, can improve the tensile strength and the snappiness of Resins, epoxy effectively.
Background technology
Concrete paint is to carry out application at concrete surface, and formation is filmed, the coating that utilizes its shielding effect to play a protective role.But the concrete surface in ocean environment is easy to be subjected to sea beaten and wearing and tearing, and is therefore, comparatively harsh to the requirement of coating.This not only needs to film and has higher compactness, also must give its good snappiness, ductility and hardness.
Epoxypaint is modal concrete paint, and it has following two characteristics: contain fat hydroxyl and ehter bond in the structure, can produce gravitation with adjacent interfaces, have very strong sticking power; Filming after the curing contains stable phenyl ring, ehter bond etc., and it is little to solidify back coating structure pore simultaneously, makes various media be difficult to infiltration.In addition, Resins, epoxy also has excellent thermostability, electrical insulation capability, and is cheap, and raw material advantage such as be easy to get is so be most widely used.
But the Resins, epoxy fragility after the film forming is big, causes that it is shock-resistant, antistripping and vibration resistance poor fatigue properties, has greatly limited its application in ocean environment.Therefore, need to explore the new method of development Resins, epoxy is carried out toughening modifying, improve its mechanical property, and apply.
Common method for toughening has at present: add disperse phase such as rubber elastomer, thermoplastic resin or liquid crystalline polymers and come toughness reinforcing in epoxy matrix; With thermosetting resin form IPN in the epoxy networks continuously, half interpenetrating network structure comes toughness reinforcing.
Goal of the invention and content
Purpose of the present invention: a kind of preparation method who is used for the polyether modified epoxy epoxy resins of concrete paint is provided.With the Resins, epoxy of this method modification, have higher snappiness, can form filming of fine and close, good toughness after the curing, shock-resistance is better, thereby improves antiseptic property.
Technical scheme of the present invention is: adopt polyethers that Resins, epoxy is carried out toughening modifying.
Technology contents of the present invention is: at first Resins, epoxy and vinylformic acid generation ring-opening reaction are made epoxy acrylic resin, then, vulcabond and polyethers generation addition reaction are made isocyanate terminated performed polymer, at last, with isocyanate terminated performed polymer and epoxy acrylic resin generation crosslinking reaction, formed a kind of interpenetrating type network polymer, i.e. the polyether modified epoxy epoxy resins.
Concrete preparation technology divides three to implement suddenly step by step:
1. catalyzer, stopper and vinylformic acid mixed solution are added in the Resins, epoxy, ring-opening reaction generates epoxy acrylic resin;
Wherein, the consumption of vinylformic acid and Resins, epoxy reaction is designated as 1 mole of epoxy group(ing) and 1～1.2 mol propylene acid-respons respectively according to the amount of substance of vinylformic acid and epoxy group(ing);
2. under nitrogen protection, vulcabond and polyethers are carried out addition reaction, obtain isocyanate terminated performed polymer;
Wherein, the consumption of polyethers and the consumption of vulcabond be respectively by the amount and the isocyanate group amount of substance of its contained hydroxylated material, is designated as 1 mole of hydroxyl with 1.1～2.0 moles of isocyanate group;
3. the epoxy acrylic resin that 1. isocyanate terminated performed polymer that 2. step is made and step make behind the uniform mixing, adds linking agent and chainextender in proportion, and reaction generates interpenetrating type network polymer, i.e. polyether modified epoxy epoxy resins.
1. in the ring-opening reaction, catalyst consumption (quality) is 0.2～0.6% of a reactant total mass to described step, and preferable amount (quality) is 0.4%; The consumption of stopper (quality) is 0.2～1.0% of a reactant total mass, and preferable amount (quality) is 0.5～0.8%.
3. in the IPN polyreaction, the consumption of linking agent (quality) is 0.05～0.15% of a reactant total mass to described step, and preferable amount (quality) is 0.10%; The consumption of chainextender (quality) is 0.03～0.10% of a reactant total mass, and preferable amount (quality) is 0.06%.
Among the above-mentioned preparation method, step ring-opening reaction temperature 1. is 85～98 ℃; 2. addition reaction temperature of step is 70～95 ℃; Step 3. IPN polymeric reaction temperature is 60～95 ℃.
Among the above-mentioned preparation method, described step 1. concrete operations is: the mixed solution of vinylformic acid and catalyzer, stopper slowly is added dropwise in the Resins, epoxy, and the dropping time is controlled at 0.5～1h; The ring-opening reaction time is 3～6h, when the acid number in the survey system is lower than 10mgKOH/g, and cooling discharge.Described step 2. concrete operations is: earlier polyethers is vacuumized dehydration 0.5～2h, then, under nitrogen protection, slowly be added dropwise to vulcabond, the dropping time is controlled at 0.2～0.8h; The addition reaction time is 2～3h; Described step 3. IPN polymerization reaction time is 0.5～1h.
Among the above-mentioned preparation method, described catalyzer is triethyl benzyl ammonia chloride, triethyl benzyl brometo de amonio and N, a kind of or its combination in the N-dimethyl Bian amine; Stopper is a kind of or its combination in Resorcinol, MEHQ and the p methoxy phenol; Linking agent is a TriMethylolPropane(TMP); Chainextender is 1, the 4-butyleneglycol.
Among the above-mentioned preparation method, described Resins, epoxy is bisphenol A type epoxy resin, particularly micromolecular bisphenol A type epoxy resin, and epoxy equivalent (weight) is between 180g/mol-1000g/mol; Described polyethers is polyether glycol (PPG), and representative has N-210, N-220 and N-204; Described vulcabond is coating aromatic series, aliphatic diisocyanate, and typical example has tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
The present invention compared with prior art has following significant technique effect:
In the technical solution of the present invention, the epoxy acrylic resin that vinylformic acid and Resins, epoxy ring-opening reaction make, contain aromatic ring and side position hydroxyl in the molecular structure, can improve molecular adhesion power, and the oxyethyl group of introducing in the molecular structure can increase the rotatory and the kindliness of molecular structure; Polyethers and vulcabond generation addition reaction, the performed polymer that contains isocyanate terminated base that makes, ammonia ester bond, ester bond have been formed, then with the epoxy acrylic resin generation latex interpenetrating polymerization reaction that contains a plurality of hydroxyls, this network polymer is because internetwork mutual entanglement, force mutual appearance, synergy, make polymkeric substance have excellent flexibility, the ester bond that contains in the polymkeric substance can improve the snappiness of polymkeric substance simultaneously, and the epoxy group(ing) of ammonia ester bond, hydroxyl and reservation can improve the sticking power of polymkeric substance.
In addition, in preparation process, adjust some technical qualification in the building-up process, as regulate the ratio of hydroxyl and isocyanate group, adjust the molecular weight of Resins, epoxy etc., but the degree of crosslinking of equal telomerized polymer, thereby performances such as the snappiness of telomerized polymer, sticking power are to satisfy the different demand in market.
Description of drawings
Fig. 1 is the section SEM photo of the modified epoxy of the inventive method preparation.
Embodiment
The present invention is by the affected further specific descriptions of following embodiment, but is not limited to this.Except as otherwise noted, the ratio of embodiment represents with mass percent that all the used raw material of embodiment all can be buied by commercial sources.
Embodiment 1:
(1) preparation of epoxy acrylic resin
Resins, epoxy 400g (epoxy equivalent (weight) 213g/mol-244g/mol) is added in the reactor, stirring is warmed up to 95 ℃, the mixed solution of dropwise addition of acrylic acid 140g, catalyzer triethyl benzyl ammonia chloride 3.24g, hydroquinone of polymerization retarder 2g, about 0.5h of dropping time, stirring reaction 4h, reaction finishes the acid number of back survey system, treats that acid number is less than 10mgKOH/g, cooling, discharging.
(2) preparation of isocyanate terminated performed polymer
In reactor, add polyethers [PPG; N-210 (average molecular mass Mn=1000g/mol)] 300g; heating vacuumizes dehydration 50min; under protection of nitrogen gas, slowly drip tolylene diisocyanate (TDI) 96g; temperature of reaction is controlled at about 80 ℃; stirring reaction 2h, cooling discharge obtains isocyanate terminated performed polymer.
(3) preparation of polyether modified epoxy epoxy resins
Isocyanate terminated performed polymer and the epoxy acrylic resin ratio in 3: 7 (mass ratio) is added in the reactor, epoxy acrylic resin 420g, isocyanate terminated performed polymer 180g, chainextender 1,4-butyleneglycol (BOD) 0.36g, linking agent TriMethylolPropane(TMP) (TMP) 0.6g, mix and be positioned over the 30min that outgases in 80 ℃ of vacuum drying ovens again, normal temperature solidifies 4h down, heats 50 ℃ then and solidifies 3h, obtains interpenetrating net polymer.
The section SEM photo of gained interpenetrating net polymer as shown in Figure 1.As can be seen from the figure, elastic component around the sample is stretched or produces the cavityization, the surface of fracture structure has less concavo-convex, this concavo-convex empty structure makes material crackle and crack in bearing the breaking-down process of load must be bondd by fine, thereby the explanation polymkeric substance shows significantly ductile rupture feature.
Detect according to standard GB/T 528-1998, the tensile strength of Resins, epoxy is 22.5MPa, and the improved Resins, epoxy stretching of present method intensity is 55.24MPa, has improved 2.5 times than pure epoxy resin intensity.
Detect according to standard GB/T 1731-1993, the snappiness of Resins, epoxy is 1 grade, and the snappiness of the improved Resins, epoxy of present method is the 3-4 level, has improved its snappiness greatly.
Other embodiment preparation method is with embodiment 1, and concrete parameter sees the following form.
Claims (10)
1. preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating, it is characterized in that, this method at first makes epoxy acrylic resin with Resins, epoxy and vinylformic acid generation ring-opening reaction, then, vulcabond and polyethers generation addition reaction are made isocyanate terminated performed polymer, last, with isocyanate terminated performed polymer and epoxy acrylic resin generation crosslinking reaction, formed a kind of interpenetrating type network polymer, i.e. the polyether modified epoxy epoxy resins;
Concrete preparation technology divided for three steps implemented:
1. catalyzer, stopper and vinylformic acid mixed solution are added in the Resins, epoxy, ring-opening reaction generates epoxy acrylic resin;
Wherein, the consumption of vinylformic acid and Resins, epoxy reaction is designated as 1 mole of epoxy group(ing) and 1～1.2 mol propylene acid-respons respectively according to the amount of substance of vinylformic acid and epoxy group(ing);
2. under nitrogen protection, vulcabond and polyethers are carried out addition reaction, obtain isocyanate terminated performed polymer;
Wherein, the consumption of polyethers and the consumption of vulcabond be respectively by the amount and the isocyanate group amount of substance of its contained hydroxylated material, is designated as 1 mole of hydroxyl with 1.1～2.0 moles of isocyanate group;
3. described isocyanate terminated performed polymer and epoxy acrylic resin in proportion behind the uniform mixing, are added linking agent and chainextender, reaction generates interpenetrating type network polymer, i.e. polyether modified epoxy epoxy resins.
2. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1 is characterized in that, 1. in the ring-opening reaction, catalyst consumption (quality) is 0.2～0.6% of a reactant total mass to described step; The consumption of stopper (quality) is 0.2～1.0% of a reactant total mass.
3. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 2 is characterized in that, 1. in the ring-opening reaction, catalyst consumption (quality) is 0.4% of a reactant total mass to described step; The consumption of stopper (quality) is 0.5～0.8% of a reactant total mass.
4. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1, it is characterized in that, described step is 3. in the IPN polyreaction, the consumption of linking agent (quality) is 0.05～0.15% of a reactant total mass, and the consumption of chainextender (quality) is 0.03～0.10% of a reactant total mass.
5. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 4 is characterized in that, 3. in the IPN polyreaction, the consumption of linking agent (quality) is 0.10% of a reactant total mass to described step; The consumption of chainextender (quality) is 0.06% of a reactant total mass.
6. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1 is characterized in that, described catalyzer is triethyl benzyl ammonia chloride, triethyl benzyl brometo de amonio and N, a kind of or its combination in the N-dimethyl Bian amine; Stopper is a kind of or its combination in Resorcinol, MEHQ and the p methoxy phenol; Linking agent is a TriMethylolPropane(TMP); Chainextender is 1, the 4-butyleneglycol.
7. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1 is characterized in that, the described step 1. temperature of ring-opening reaction is 85～98 ℃; The described step 2. temperature of addition reaction is 70～95 ℃; The described step 3. temperature of IPN polyreaction is 60～95 ℃.
8. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1, it is characterized in that, described step 1. concrete operations is: the mixed solution of vinylformic acid and catalyzer, stopper slowly is added dropwise in the Resins, epoxy, and the dropping time is controlled at 0.5h～1h; The ring-opening reaction time is 3h～6h, when the acid number in the survey system is lower than 10mgKOH/g, and cooling discharge; Described step 2. concrete operations is: earlier polyethers is vacuumized dehydration 0.5h～2h, then, under nitrogen protection, slowly be added dropwise to vulcabond, the dropping time is controlled at 0.2h～0.8h, and the addition reaction time is 2h～3h; Described step 3. IPN polymerization reaction time is 0.5h～1h.
9. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 1 is characterized in that, the 1. used Resins, epoxy of described step is bisphenol A type epoxy resin; The 2. used polyethers of described step adopts polyether glycol (PPG); Vulcabond is coating aromatic series, aliphatic diisocyanate.
10. the preparation method who is used for the polyether modified epoxy epoxy resins of maritime concrete coating as claimed in claim 9 is characterized in that described Resins, epoxy is micromolecular bisphenol A type epoxy resin, and epoxy equivalent (weight) is between 180g/mol-1000g/mol; Described polyether glycol (PPG) is N-210, N-220 and N-204; Described aromatic series, aliphatic diisocyanate are tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
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| CN2011101245106A CN102286137A (en) | 2011-05-06 | 2011-05-06 | Preparation method of polyether modified epoxy resins used for marine concrete paint |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670229A (en) * | 2016-04-07 | 2016-06-15 | 主义 | Technology for preparing epoxy-resin-polymer grouting liquid |
| CN105906260A (en) * | 2016-04-07 | 2016-08-31 | 主义 | Preparation method of epoxy resin polymer concrete |
| CN111794548A (en) * | 2020-06-30 | 2020-10-20 | 中国科学院海洋研究所 | Reinforced concrete crack-following coating system and anti-corrosion application thereof |
| CN115521701A (en) * | 2022-10-11 | 2022-12-27 | 深圳砺剑博纳科技有限公司 | Corrosion-resistant anti-aging coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804672A (en) * | 1993-05-26 | 1998-09-08 | Henkel Kommanditgesellschaft Auf Aktien | Thermally crosslinkable heat-sealing adhesive |
| CN1710002A (en) * | 2005-06-16 | 2005-12-21 | 武汉科利尔化工有限公司 | Water-based polyurethane resin and its electrophoretic paint composition and preparing method |
| CN101125927A (en) * | 2007-07-23 | 2008-02-20 | 孝感学院 | Polyurethane interpenetrating network polymer, preparation method and use thereof |
-
2011
- 2011-05-06 CN CN2011101245106A patent/CN102286137A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804672A (en) * | 1993-05-26 | 1998-09-08 | Henkel Kommanditgesellschaft Auf Aktien | Thermally crosslinkable heat-sealing adhesive |
| CN1710002A (en) * | 2005-06-16 | 2005-12-21 | 武汉科利尔化工有限公司 | Water-based polyurethane resin and its electrophoretic paint composition and preparing method |
| CN101125927A (en) * | 2007-07-23 | 2008-02-20 | 孝感学院 | Polyurethane interpenetrating network polymer, preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 包罗涛: ""紫外光固化胶粘剂的制备及性能的研究"", 《"紫外光固化胶粘剂的制备及性能的研究"-华南理工大学硕士学位论文》, 10 March 2009 (2009-03-10) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670229A (en) * | 2016-04-07 | 2016-06-15 | 主义 | Technology for preparing epoxy-resin-polymer grouting liquid |
| CN105906260A (en) * | 2016-04-07 | 2016-08-31 | 主义 | Preparation method of epoxy resin polymer concrete |
| CN105670229B (en) * | 2016-04-07 | 2019-02-05 | 主义 | A kind of preparation process of epoxide resin polymer grouting liquid |
| CN111794548A (en) * | 2020-06-30 | 2020-10-20 | 中国科学院海洋研究所 | Reinforced concrete crack-following coating system and anti-corrosion application thereof |
| CN111794548B (en) * | 2020-06-30 | 2022-03-15 | 中国科学院海洋研究所 | Reinforced concrete crack-following coating system and anti-corrosion application thereof |
| CN115521701A (en) * | 2022-10-11 | 2022-12-27 | 深圳砺剑博纳科技有限公司 | Corrosion-resistant anti-aging coating and preparation method thereof |
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Application publication date: 20111221 |