CN103601868A - Method for preparing terminated epoxypolyurethane through grease dimer acids - Google Patents
Method for preparing terminated epoxypolyurethane through grease dimer acids Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
- C08G18/686—Unsaturated polyesters containing cyclic groups containing cycloaliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for preparing terminated epoxypolyurethane through a grease dimer acid. The method comprises the following steps: 1, obtaining terminated hydroxypolyester polyol between the grease dimer acid and dihydric alcohol under the action of an esterification catalyst; 2, obtaining a terminated isocyanopolyurethane prepolymer between the terminated hydroxypolyester polyol and isocyanate under the action of a polyurethane catalyst; and 3, reacting the terminated isocyanopolyurethane prepolymer and a terminated hydroxyepoxy compound at a certain temperature, and obtaining a high-elasticity terminated epoxypolyurethane resin. According to the prepared terminated epoxypolyurethane, the dimer acid synthesized by waste oil is taken as a raw material, the cost is low, and the obtained terminated epoxypolyurethane has high strength and extremely high elongation and is an excellent structure modified resin for a bisphenol A epoxy resin structure adhesive.
Description
Technical field
The invention belongs to high-elasticity epoxy resin field, be specifically related to a kind of preparation method of epoxy-terminated polyurethane.
Background technology
Epoxy resin has the characteristics such as good cohesiveness, physical strength, electrical insulating property and is widely used in each industrial circle of national economy, but its second-order transition temperature is high, property is crisp, the textural defect such as shock strength is low, its application is subject to certain restrictions, is difficult to meet the requirement of many engineering increasingly stringents.From structure, improve the snappiness of epoxy resin, become the hot order problem of epoxy resin utilisation technology.
The flexibility of bisphenol A epoxide resin matrix material, solves by the polymkeric substance that grafting in its structure has a flexible structure conventionally.Lin Xin hat waits and has applied for that a kind of fatty acid modified epoxy resin patent (CN103073701A), this modified epoxy can increase the snappiness of epoxy resin-cured product, but can not significantly improve bisphenol A epoxide resin cured product elongation at break; Han Xiao family etc. has announced a kind of patent (CN85101895) of butyronitrile hydroxyl modified epoxy, utilize butyronitrile hydroxyl-toluene diisocyanate prepolymer, directly add epoxy composite material system to increase the snappiness of system, because end isonitrile based structures is easy to moisture absorption, storage requires high, is unfavorable for large-scale promotion use; Hu Shaokun (" specialty elastomer goods ", 30(5), 2009) reported the research of carboxyl liquid acrylonitrile butadiene rubber modified epoxy, epoxy resin-cured product elongation has been up to 74%, be subject to the impact that carboxyl butyronitrile price and smell are heavy, this system can only be used in compared with high value added product.
Summary of the invention
In order to solve the bisphenol A epoxide resin modified system of prior art existence, there is the shortcoming that properties-correcting agent price is higher, elongation at break is not high, the invention discloses a kind of method of being prepared epoxy-terminated polyurethane by grease dimeracid, take grease dimeracid as body material, there is the advantages such as cheap, environmental protection, raw material be renewable.
Technical scheme of the present invention is: a kind of method of being prepared epoxy-terminated polyurethane by grease dimeracid, comprise the steps: step 1, prepare hydroxyl telechelic polyester polyvalent alcohol: grease dimeracid and excess glycol, under esterifying catalyst effect, esterification occurs, excess glycol is sloughed in decompression, obtains hydroxyl telechelic polyester polyvalent alcohol; Step 2, preparation end isocyano-base polyurethane prepolymer for use as: hydroxyl telechelic polyester polyvalent alcohol and vulcabond, under catalysts for polyurethanes effect, addition reaction occurs, and obtains holding isocyano-base polyurethane prepolymer for use as; Step 3, prepare epoxy-terminated polyurethane resin: end isocyano-base polyurethane prepolymer for use as is reacted to temperature-stable with being uniformly mixed under terminal hydroxy group epoxy compounds room temperature, be warming up to 50～65 ℃ of left and right, react to the acid number of system and drop to below 2mgKOH/g, obtain brown color thickness epoxy-terminated polyurethane resin; Described terminal hydroxy group epoxy compounds is 1-hydroxyl-2,3 R-GLYCIDOLs.
Described grease dimeracid is any one in soybean oil dimer (fatty acid) yl, Oleum Gossypii semen dimer (fatty acid) yl or tung oil dimer (fatty acid) yl, and ring texture is not less than 85% by mass.
Described esterifying catalyst is a kind of in tetrabutyl titanate, stannous octoate, tosic acid, zinc oxide.
Dibasic alcohol used is propylene glycol, glycol ether, and neopentyl glycol, ethylene glycol is arbitrary.
Vulcabond used is Toluene-2,4-diisocyanate, 4-vulcabond or 4,4`-diphenylmethanediisocyanate.
Catalysts for polyurethanes used is stannous octoate, and dibutyl tin laurate is sad sub-plumbous arbitrary.
Beneficial effect:
1. the raw oil material dimer (fatty acid) yl that the present invention adopts, derives from the natural fats and oils such as soybean oil, Oleum Gossypii semen or tung oil, has renewable, the environmentally friendly and lower-price characteristic of raw material sources.
2. compare with the direct Graft Epoxy Resin structure of direct carboxylated compound, this structural system is easy to form and be separated at solidification process, can not only improve the elongation at break of epoxy resin solidifying system, also can guarantee the physical strength of cured product simultaneously.
Embodiment
Following examples are to further illustrate of the present invention, are not limitations of the present invention.
A method of being prepared epoxy-terminated polyurethane by grease dimer (fatty acid) yl, comprises the steps:
Step 1, grease dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.1～2.5 in dimer (fatty acid) yl and dibasic alcohol mol ratio adds dibasic alcohol, adds 0.1%～0.5% esterifying catalyst of total mass, starts stirring, be warming up to gradually 180～200 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol; Described grease dimer (fatty acid) yl is any one in soybean oil dimer (fatty acid) yl, Oleum Gossypii semen dimer (fatty acid) yl or tung oil dimer (fatty acid) yl, and by mass, ring texture is not less than 85%; Described dibasic alcohol comprises propylene glycol, glycol ether, neopentyl glycol, ethylene glycol.Described esterifying catalyst is isocaprylic acid lead, stannous octoate, tosic acid, zinc oxide, and raw material is easy to buying.
Step 2, a certain amount of vulcabond is placed in to reaction flask, adding in batches total mass is the polyester polyols alcohol ester of 1.8～2.2 times of vulcabond quality, add the catalysts for polyurethanes that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, be warming up to 50 ℃～60 ℃, react 1～3h, be cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as; Described catalysts for polyurethanes comprises stannous octoate, and dibutyl tin laurate is sad sub-plumbous.
Step 3, by toluene 2,4 vulcabond and 1-hydroxyl-2,3 R-GLYCIDOLs
mol ratio is the ratio of 1:1.0～1.1, end isocyano-base polyurethane prepolymer for use as and terminal hydroxy group epoxide are added in reaction flask, and stirring at room reaction 1 hour, is warming up to 50 ℃～60 ℃, continue reaction 1～3 hour, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.Described terminal hydroxy group epoxy compounds is 1-hydroxyl-2,3 R-GLYCIDOLs.
Embodiment 1
Step 1, soybean oil dimer (fatty acid) yl (production of Jiangsu Golden Horse oil technology Development Co., Ltd) is placed in to reaction flask, the ratio that is 1:2.1 in dimer (fatty acid) yl and ethylene glycol mol ratio adds ethylene glycol, add 0.1% the esterifying catalyst stannous octoate that accounts for total mass, start stirring, be warming up to gradually 180 ℃, reaction 4h, when acid number is down to 2mgKOH/g when following, under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of Toluene-2,4-diisocyanate, 4-vulcabond (TDI) is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 1.8 times of vulcabond quality, add the catalysts for polyurethanes stannous octoate that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react for some time, after equitemperature is stable, be warming up to 50 ℃, reaction 1h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, end isocyano-base polyurethane prepolymer for use as in step 2 adds 1-hydroxyl-2,3 R-GLYCIDOLs, its mole dosage and Toluene-2,4-diisocyanate, the mole dosage of 4-vulcabond is identical, and stirring at room reaction 1 hour, is warming up to 50 ℃, continue reaction 1 hour, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
This product quality indicator: color and luster (iodine colorimetric) 2-3, acid number 0.02mgKOH/g, 206 ℃ of flash-points, resistivity 2 * 10
12Ω cm.
Embodiment 2
Step 1, Oleum Gossypii semen dimer (fatty acid) yl (production of Jiangsu Golden Horse oil technology Development Co., Ltd) is placed in to reaction flask, the ratio that is 1:2.2 in dimer (fatty acid) yl and glycol ether mol ratio adds glycol ether, 0.3% the esterifying catalyst tosic acid that adds total mass, start stirring, be warming up to gradually 190 ℃, reaction 4h, when acid number is down to 2mgKOH/g when following, under the vacuum tightness of 2mmHg, moisture and excessive glycol ether are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of Toluene-2,4-diisocyanate, 4-vulcabond is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2 times of vulcabond quality, add the catalysts for polyurethanes dibutyl tin laurate that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react for some time, after equitemperature is stable, be warming up to 55 ℃, reaction 2h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, press Toluene-2,4-diisocyanate, 4-vulcabond and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.05, will hold isocyano-base polyurethane prepolymer for use as and 1-hydroxyl-2, and 3 R-GLYCIDOLs add in reaction flask, stirring at room reaction 1 hour, be warming up to 55 ℃, continue reaction 2 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 3
Step 1, tung oil dimer (fatty acid) yl (production of Chinese forest-science academy Nanjing Scientific developing head office of forest chemical institute) is placed in to reaction flask, the ratio that is 1:2.5 in dimer (fatty acid) yl and dibasic alcohol mol ratio adds neopentyl glycol, 0.5% the esterifying catalyst tetrabutyl titanate that adds total mass, start stirring, be warming up to gradually 200 ℃, reaction 4h, when acid number is down to 2mgKOH/g when following, under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, a certain amount of toluene 2,4 vulcabond are placed in to reaction flask, and adding in batches total mass is the polyester polyol of 2.2 times of vulcabond quality, add the sad sub-lead of catalysts for polyurethanes that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react, after equitemperature is stable, be warming up to 60 ℃, reaction 3h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, press toluene 2,4 vulcabond and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.1, will hold isocyano-base polyurethane prepolymer for use as and 1-hydroxyl-2, and 3 R-GLYCIDOLs add in reaction flask, stirring at room reaction 1 hour, be warming up to 60 ℃, continue reaction 2.5 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 4
Step 1, soybean oil dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.1～2.5 in dimer (fatty acid) yl and ethylene glycol mol ratio adds ethylene glycol, then adds 0.4% esterifying catalyst tosic acid of total mass, starts stirring, be warming up to gradually 190 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, a certain amount of toluene 2,4 vulcabond are placed in to reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2.1 times of vulcabond quality, add the sad sub-lead of catalysts for polyurethanes that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react for some time, after equitemperature is stable, be warming up to 52 ℃, reaction 2.5h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, press Toluene-2,4-diisocyanate, 4-vulcabond and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.05, will hold isocyano-base polyurethane prepolymer for use as and 1-hydroxyl-2, and 3 R-GLYCIDOLs add in reaction flask, stirring at room reaction 1 hour, be warming up to 58 ℃, continue reaction 2 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 5
Step 1, Oleum Gossypii semen dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.3 in Oleum Gossypii semen dimer (fatty acid) yl and propylene glycol mol ratio adds propylene glycol, adds 0.4% esterifying catalyst zinc oxide of total mass, starts stirring, be warming up to gradually 180 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of 4,4' diphenylmethanediisocyanate (MDI) is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2.0 times of vulcabond quality, add the catalysts for polyurethanes dibutyl tin laurate that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react for some time, after equitemperature is stable, be warming up to 53 ℃, reaction 3h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, by 4,4' diphenylmethanediisocyanate and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.07, will hold isocyano-base polyurethane prepolymer for use as and 1-hydroxyl-2, and 3 R-GLYCIDOLs add in reaction flask, stirring at room reaction 1 hour, be warming up to 59 ℃, continue reaction 1 hour, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 6
Step 1, tung oil dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.2 in tung oil dimer (fatty acid) yl and neopentyl glycol mol ratio adds dibasic alcohol, adds 0.1% esterifying catalyst tetrabutyl titanate of total mass, starts stirring, be warming up to gradually 200 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of 4,4' diphenylmethanediisocyanate is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2.2 times of vulcabond quality, add the catalysts for polyurethanes dibutyl tin laurate that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature, react for some time, after temperature-stable, be warming up to 55 ℃, reaction 1.5h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, by 4,4' diphenylmethanediisocyanate and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.02, will hold isocyano-base polyurethane prepolymer for use as and 1-hydroxyl-2, and 3 R-GLYCIDOLs add in reaction flask, stirring at room reaction 1 hour, be warming up to 56 ℃, continue reaction 2 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin
Embodiment 7
Step 1, soybean oil dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.3 in soybean oil dimer (fatty acid) yl and ethylene glycol mol ratio adds dibasic alcohol, adds 0.3% esterifying catalyst zinc oxide of total mass, starts stirring, be warming up to gradually 180 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of 4,4' diphenylmethanediisocyanate is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 1.8 times of vulcabond quality, add the sad sub-lead of catalysts for polyurethanes that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, under room temperature condition, react for some time, after temperature-stable, be warming up to 57 ℃, reaction 2.5h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, by 4,4' diphenylmethanediisocyanate and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.0～1.1, end isocyano-base polyurethane prepolymer for use as and terminal hydroxy group epoxide are added in reaction flask, and stirring at room reaction 1 hour, is warming up to 50 ℃～60 ℃, continue reaction 1～3 hour, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.Described terminal hydroxy group epoxy compounds is 1-hydroxyl-2,3 R-GLYCIDOLs.
Embodiment 8
Step 1, Oleum Gossypii semen dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.5 in Oleum Gossypii semen dimer (fatty acid) yl and propylene glycol mol ratio adds propylene glycol, adds 0.5% esterifying catalyst tetrabutyl titanate of total mass, starts stirring, be warming up to gradually 190 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive dibasic alcohol are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of 4,4' diphenylmethanediisocyanate is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2.0 times of vulcabond quality, add the catalysts for polyurethanes stannous octoate that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, room temperature reaction for some time, after temperature-stable, be warming up to 50 ℃～60 ℃, reaction 3h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, by 4,4' diphenylmethanediisocyanate and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.02, end isocyano-base polyurethane prepolymer for use as and terminal hydroxy group epoxide are added in reaction flask, and stirring at room reaction 1 hour, is warming up to 56 ℃, continue reaction 1.5 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 9
Step 1, soybean oil dimer (fatty acid) yl is placed in to reaction flask, the ratio that is 1:2.4 in soybean oil dimer (fatty acid) yl and glycol ether mol ratio adds glycol ether, adds 0.3% esterifying catalyst zinc oxide of total mass, starts stirring, be warming up to gradually 195 ℃, reaction 4h, is down to 2mgKOH/g when following when acid number, and under the vacuum tightness of 2mmHg, moisture and excessive glycol ether are removed in underpressure distillation, filtered while hot, obtains hydroxyl telechelic polyester polyvalent alcohol;
Step 2, by a certain amount of 4,4'-diphenylmethanediisocyanate is placed in reaction flask, and adding in batches total mass is the hydroxyl telechelic polyester polyvalent alcohol of 2.1 times of vulcabond quality, add the catalysts for polyurethanes that is equivalent to hydroxyl telechelic polyester polyvalent alcohol quality 0.2%, start stirring, room temperature reaction for some time, after temperature-stable, be warming up to 55 ℃, reaction 1h, is cooled to room temperature, must hold isocyano-base polyurethane prepolymer for use as;
Step 3, by 4,4' diphenylmethanediisocyanate and 1-hydroxyl-2, the ratio that 3 R-GLYCIDOL mol ratios are 1:1.06, end isocyano-base polyurethane prepolymer for use as and terminal hydroxy group epoxide are added in reaction flask, and stirring at room reaction 1 hour, is warming up to 58 ℃, continue reaction 3 hours, obtain brown color thickness snappiness epoxy-terminated polyurethane resin.
Embodiment 10
Snappiness epoxy-terminated polyurethane of the present invention (EPU)/bisphenol A epoxide resin (EP) (the market trade mark 128) mixes according to a certain percentage, take polyetheramine (PAM) (market trade mark D230) and N-aminoethyl piperazine (AEP) (mass ratio is 15/7) solidifying agent, in mass ratio for 100:25-30 mixes, self-vulcanizing 7 days, or 80 ℃ solidify 6 hours, the tensile strength of cured product and elongation at break can significantly improve tensile strength and the elongation at break of bisphenol A epoxide resin curing system in Table 1. snappiness epoxy-terminated polyurethane resins, over-all properties is better than carboxyl butyronitrile modified epoxy.
Table 1 snappiness epoxy-terminated polyurethane curing system mechanical property
Claims (6)
1. a method of being prepared epoxy-terminated polyurethane by grease dimeracid, it is characterized in that, comprise the steps: step 1, prepare hydroxyl telechelic polyester polyvalent alcohol: grease dimeracid and excess glycol, under esterifying catalyst effect, esterification occurs, excess glycol is sloughed in decompression, obtains hydroxyl telechelic polyester polyvalent alcohol; Step 2, preparation end isocyano-base polyurethane prepolymer for use as: hydroxyl telechelic polyester polyvalent alcohol and vulcabond, under catalysts for polyurethanes effect, addition reaction occurs, and obtains holding isocyano-base polyurethane prepolymer for use as; Step 3, prepare epoxy-terminated polyurethane resin: end isocyano-base polyurethane prepolymer for use as is reacted to temperature-stable with being uniformly mixed under terminal hydroxy group epoxy compounds room temperature, be warming up to 50～65 ℃ of left and right, react to the acid number of system and drop to below 2mgKOH/g, obtain brown color thickness epoxy-terminated polyurethane resin; Described terminal hydroxy group epoxy compounds is 1-hydroxyl-2,3 R-GLYCIDOLs.
2. the method for being prepared epoxy-terminated polyurethane by grease dimeracid as claimed in claim 1, it is characterized in that, described grease dimeracid is any one in soybean oil dimer (fatty acid) yl, Oleum Gossypii semen dimer (fatty acid) yl or tung oil dimer (fatty acid) yl, and ring texture is not less than 85% by mass.
3. the method for being prepared epoxy-terminated polyurethane by grease dimeracid as claimed in claim 1, is characterized in that, described esterifying catalyst is a kind of in tetrabutyl titanate, stannous octoate, tosic acid, zinc oxide.
4. the method for being prepared epoxy-terminated polyurethane by grease dimeracid as claimed in claim 1, is characterized in that, dibasic alcohol used is propylene glycol, glycol ether, and neopentyl glycol, ethylene glycol is arbitrary.
5. the method for being prepared epoxy-terminated polyurethane by grease dimeracid as claimed in claim 1, is characterized in that, vulcabond used is Toluene-2,4-diisocyanate, 4-vulcabond or 4,4`-diphenylmethanediisocyanate.
6. the method for being prepared epoxy-terminated polyurethane by grease dimeracid as claimed in claim 1, is characterized in that, catalysts for polyurethanes used is stannous octoate, and dibutyl tin laurate is sad sub-plumbous arbitrary.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114644746A (en) * | 2022-04-21 | 2022-06-21 | 韶关东森合成材料有限公司 | Polyurethane modified epoxy resin and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218778A (en) * | 2015-10-21 | 2016-01-06 | 中山大桥化工集团有限公司 | A kind of epoxy terminated waterborne polyurethane resin and preparation method thereof |
| CN111269381A (en) * | 2018-12-05 | 2020-06-12 | 万华化学集团股份有限公司 | Thermoplastic polyurethane for color concentrate carrier |
| CN111187393A (en) * | 2020-02-19 | 2020-05-22 | 中科院广州化灌工程有限公司 | Hyperbranched epoxy resin, hyperbranched epoxy resin-based building structure adhesive, preparation and application |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
| CN114644746A (en) * | 2022-04-21 | 2022-06-21 | 韶关东森合成材料有限公司 | Polyurethane modified epoxy resin and preparation method and application thereof |
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