A kind of dimer acid polyester polyhydric alcohols and preparation method thereof
Technical field
The present invention relates to a kind of polyvalent alcohol and preparation method thereof, more specifically to a kind of dimer acid polyester polyhydric alcohols and preparation method thereof.
Background technology
Polymer polyatomic alcohol is one of main raw material of synthesis of polyurethane, generally be divided into polyether-type and polyester type, polyester polyol is compared with widely used polyether glycol in the market, heatproof, wear-resisting, oil resistant and physical strength height take advantage, and therefore demonstrate its characteristic in goods such as polyurethane foam material, synthetic leather, coating, bonding agent, elastomerics and developed.Particularly in the polyether(poly)urethane rigid foam material of widely applying in recent years, add a certain proportion of polyester polyol, can improve the intensity of material by a relatively large margin, thereby can significantly reduce the production cost of polyurethane rigid foam material; Because polyester type foam material thermal conductivity is little, the thermal and insulating performance excellence is used widely at aspects such as piping insulation and heat-insulatings at present.
Polyester polyol is formed by diprotic acid and polyol condensating usually, and wherein diprotic acid can be aliphatic dibasic acid or aromatic acid.Dimeracid is the diprotic acid that unsaturated fatty acids generates by the Diels-Alder reaction under certain condition, has thermostability preferably.Contain the alkyl of two carboxyls and two long-chains in the dimeracid molecule, its chemical property is similar to lipid acid.The polyester that structure that dimeracid is special and chemical activity make itself and the reaction of polyvalent alcohol alcohol is being better than the less diacid of molecular weight aspect flexibility, shock-resistance and the water tolerance.
Patent 200710021803.5 adopts the method for transesterify, and dimer (fatty acid) yl methyl esters and polyvalent alcohol that the fatty acid methyl ester that the vegetables oil alcoholysis is obtained carries out generating after the thermopolymerization obtain fatty polyol dimer by transesterify.The dimer acid polyester polyhydric alcohols that this method is produced is applied in the urethane foam, and resistance toheat, intensity, the resistance to tearing of product are obviously improved.But this technology is gone through the steps such as recovery of alcoholysis, thermopolymerization, distillation, transesterify and unnecessary alcohol, and technology is complicated, and by product is more, and the relative molecular mass of gained polyester polyol product is lower, and range of application is restricted.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that above-mentioned prior art exists, a kind of dimer acid polyester polyhydric alcohols is provided, the acid number of this dimer acid polyester polyhydric alcohols is that 0.5~4mgKOH/g, hydroxyl value are 60~500mgKOH/g.
The present invention simultaneously also provides the preparation method of this dimer acid polyester polyhydric alcohols, and this method is easy to operate and product performance stable.
The present invention is achieved by the following technical solutions;
The preparation method of dimer acid polyester polyhydric alcohols of the present invention may further comprise the steps:
(1) dimeracid and polyvalent alcohol are added in the reactor, the molar ratio of dimeracid and polyvalent alcohol is 1: 1~1: 4, adds catalyzer and band aqua simultaneously, under nitrogen protection, stir and backflow, be warming up to 100~160 ℃ gradually, be controlled under this temperature of reaction, slowly refluxed 2~4 hours;
(2) continue heating when the temperature of reactor reaches 140~170 ℃, water begins to be told in room temperature, is warming up to 170~220 ℃ then rapidly, and insulation reaction 2~6 hours is all steamed up to moisture under this temperature, continue to reflux 0.5~2 hour, stop heating;
When (3) temperature is reduced to 80 ℃, closes nitrogen and begin underpressure distillation and open heating, be warming up to 120~180 ℃, insulation reaction is 1~2 hour under this temperature, when not having small-molecule substance and steam, continues to reflux 0.5 hour, stops heating;
(4) vacuum state cools off reaction product down, when temperature is reduced to 80 ℃, pours out reaction product, obtains the dimer acid polyester polyhydric alcohols of light brown.
In the preparation method of dimer acid polyester polyhydric alcohols of the present invention, the dimeracid described in its step (1) is industrial rank, and purity is 75~85%; Described polyvalent alcohol is preferably ethylene glycol, glycol ether, glycerol, tetramethylolmethane, polyoxyethylene glycol, 1,4-butyleneglycol, 1, the mixture of one or more in the 2-propylene glycol; Described catalyzer is preferably the vitriol oil, tosic acid, tetrabutyl titanate, tin protochloride or dibutyl tin laurate, and catalyst consumption is preferably 0.1~0.5% of dimeracid and polyvalent alcohol quality summation; Described band aqua is preferably toluene or dimethylbenzene, and add-on is preferably 5%~10% of reactant cumulative volume; Slow return time described in its step (1) is preferably 2 hours, and temperature of reaction is preferably 150~160 ℃.
Among the preparation method of dimer acid polyester polyhydric alcohols of the present invention, the time of the insulation reaction described in its step (2) is preferably 5~6 hours, and temperature of reaction is preferably 170~200 ℃; The pressure of the underpressure distillation described in its step (3) is preferably 10~60mmHg.
By the dimer acid polyester polyhydric alcohols of method preparation of the present invention, its acid number is that 0.5~4mgKOH/g, hydroxyl value are 60~500mgKOH/g, and product is a flowability light brown transparence liquid preferably.The present invention adopt acid number calculate reaction esterification yield, the product esterification yield that present method makes is greater than 98%.
The present invention compared with prior art has following beneficial effect:
The polymerization technique that the present invention adopts is easy, and intermediate steps is few, the transformation efficiency height, good reproducibility, cost is low, and environmental pollution is little and can be at any time at reaction process sampling and measuring acid number, reaction process is controlled, thereby the molecular weight of regulating polyester polyol satisfies different service requirementss.The polyester polyol that the present invention makes can be used for preparing polyurethane elastomer, foam, coating etc., is the very strong invention of a kind of practicality.
Embodiment
Below by specific embodiment explanation the present invention, but the present invention not merely is defined in these embodiment, used dimeracid is industrial rank among the embodiment, purity is 75~85%.
Embodiment 1
With 111.2g dimeracid and 98.0g molecular weight is that 400 polyoxyethylene glycol adds and has in the reactor of agitator, condensation division box, nitrogen protection, thermometer and heating jacket, add the 0.6276g tosic acid simultaneously as catalyzer, be warming up to 160 ℃ gradually, constantly stir in the temperature-rise period, make two component thorough mixing, obtain shallow yellow transparent solution, control reaction temperature is 160 ℃, and slowly reflux time is 2 hours; This moment, water began to be told in room temperature, was warming up to 180 ℃ then rapidly, and insulation reaction is 2 hours under this temperature, was all steamed substantially up to moisture, continued to reflux 0.5 hour, stopped heating; When being reduced to 80 ℃, temperature begins underpressure distillation, vacuum tightness is 40mmHg, when temperature recovery to 110 ℃, water, excessive small-molecule substances such as polyvalent alcohol begin to be steamed, when temperature recovery to 180 ℃, excessive reactant and small molecules are steamed, and stir 1 hour under this temperature, when not having small-molecule substance substantially and steaming, continue to reflux 0.5 hour; Vacuum state is the cooling reaction product down, when temperature is reduced to 80 ℃, pours out reaction product, obtains brown transparence polyester polyol.After measured, the acid number of product is 3.28mgKOH/g, and hydroxyl value is 60mgKOH/g.
Embodiment 2
74.0g dimeracid and the adding of 29.7g glycol ether are had in the reactor of agitator, condensation division box, nitrogen protection, thermometer and heating jacket, add the 0.3106g tosic acid simultaneously and be warming up to 140 ℃ gradually as catalyzer, constantly stir in the temperature-rise period, make two component thorough mixing, obtain shallow yellow transparent solution, control reaction temperature is 140 ℃, and slowly reflux time is 1 hour; Continue heating when the temperature of reactor reaches 150 ℃, water begins to be told in room temperature, is warming up to 170~180 ℃ then rapidly, and insulation reaction 4 hours is all steamed substantially up to moisture under this temperature, continues to reflux 0.5 hour, stops to heat; Can survey an acid number every one hour in the reaction process, when acid number no longer reduces, stop heating, temperature begins underpressure distillation when being reduced to 80 ℃, vacuum tightness is 20mmHg, when temperature recovery to 160 ℃, excessive small molecules such as glycol ether are steamed, under this temperature, stirred 1 hour, and when not having small-molecule substance substantially and steaming, continued to reflux 0.5 hour; Vacuum state is the cooling reaction product down, when temperature is reduced to 80 ℃, pours out reaction product, obtains red-brown transparence polyester polyol.After measured, the acid number of product is 3.62mgKOH/g, and hydroxyl value is 85mgKOH/g.
Embodiment 3
93.3g dimeracid and the adding of 37.6g glycol ether are had in the reactor of agitator, condensation division box, nitrogen protection, thermometer and heating jacket, add simultaneously the 0.3912g tosic acid as catalyzer and 20ml dimethylbenzene as the band aqua, be warming up to 140 ℃ gradually, constantly stir in the temperature-rise period, make two component thorough mixing, obtain shallow yellow transparent solution, control reaction temperature is 140 ℃, and slowly reflux time is 2 hours; Continue heating when the temperature of reactor reaches 150 ℃, water begins to be told in room temperature, is warming up to 170 ℃ then rapidly, and insulation reaction 2 hours is all steamed substantially up to moisture under this temperature, continues to reflux 0.5 hour, stops to heat; Temperature begins underpressure distillation when being reduced to 80 ℃, vacuum tightness is 40mmHg, and when temperature recovery to 160 ℃, excessive small molecules such as glycol ether are steamed, and stirs 1 hour under this temperature, when not having small-molecule substance substantially and steaming, continues to reflux 0.5 hour; Vacuum state is the cooling reaction product down, when temperature is reduced to 80 ℃, pours out reaction product, obtains brown transparence polyester polyol.After measured, the acid number of product is 3.35mgKOH/g, and hydroxyl value is 80mgKOH/g.
Embodiment 4
59.2g dimeracid and the adding of 31.0g glycol ether are had in the reactor of agitator, condensation division box, nitrogen protection, thermometer and heating jacket, add simultaneously the 0.3610g tin protochloride as catalyzer and 15ml dimethylbenzene as the band aqua, be warming up to 160 ℃ gradually, constantly stir in the temperature-rise period, make two component thorough mixing, obtain shallow yellow transparent solution, control reaction temperature is 160 ℃, and slowly reflux time is 1 hour; Continue heating when the temperature of reactor reaches 170 ℃, water begins to be told in room temperature, is warming up to 200 ℃ rapidly, and insulation reaction 6 hours is all steamed substantially up to moisture under this temperature, continues to reflux 0.5 hour, stops to heat; Temperature begins underpressure distillation when being reduced to 80 ℃, vacuum tightness is 20mmHg, and when temperature recovery to 180 ℃, excessive small molecules such as glycol ether are steamed, and stirs 1 hour under this temperature, when not having small-molecule substance substantially and steaming, continues to reflux 0.5 hour; Vacuum state is the cooling reaction product down, when temperature is reduced to 80 ℃, pours out reaction product, obtains light brown transparence polyester polyol.After measured, the acid number of product is 1.39mgKOH/g, and hydroxyl value is 120mgKOH/g.