CN102942664A - Preparation method of hydroxyl-terminated hyperbranched polyurethane - Google Patents
Preparation method of hydroxyl-terminated hyperbranched polyurethane Download PDFInfo
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Abstract
The invention relates to a preparation method of hydroxyl-terminated hyperbranched polyurethane. The operation steps include that 1 hydroxyl-terminated micromolecule polyhydric alcohol is dissolved in a non-proton organic solvent to obtain a hydroxyl-terminated micromolecule polyhydric alcohol solution; 2 the temperature of diisocyanate is raised to 70-90 DEG C, the hydroxyl-terminated micromolecule polyhydric alcohol solution is added, catalyst is added, and a reaction is conducted to obtain first generation hyperbranched prepolymer a1; and 3 the temperature of the first generation hyperbranched prepolymer a1 and di-alkanolamine is reduced to 0-15 DEG C, the temperature is kept, a reaction is conducted after blending, and products are separated and purified through precipitator and vacuum-dried to obtain first generation hydroxyl-terminated hyperbranched polyurethane A1. A synthesizing process is good in controllability, and the synthesized hyperbranched polyurethane is high in purity and neat in structure, contains large amount of terminated hydroxyl and is suitable for being used as a biological medicine carrier, a cross-linking agent, a viscosity modifier, a thermosetting material curing agent, a phase solubilizer, a rheological agent, thixotrope, a nucleating agent and the like.
Description
Technical field
The invention belongs to the hyperbranched polymer technical field, be specifically related to a kind of preparation method of super branched polyurethane.
Background technology
Hyper-branched polymer is with its unique molecular structure, and is soluble, contains a large amount of end groups, and molecular chain is easy entanglement not, and soltion viscosity is less and caused various countries scientists' interest.Urethane is widely applied in a lot of fields of modern society, comprise porous plastics, rubber, coating, tackiness agent etc., super branched polyurethane is compared not only more excellent aspect viscosity, solvability and film-forming properties with conventional urethane, and special functionalized application is arranged.As solid-solid phase-change energy-storage material, polymer electrolyte, shape-memory material, viscosity modifier, thermosetting material solidifying agent, phase solubilizing agent, auxiliary rheological agents, thixotrope, nucleator, active compound carriers etc., thereby how to prepare the urethane (HBPU) with dissaving structure and also caused various countries scientists' great attention.The synthetic method of hyperbranched polymer has a large amount of reports, yet because the reactive functionality of synthesis of super branched urethane monomer is extremely active.Therefore it is difficult to be synthesized with traditional method.The synthetic following methods that mainly contains of super branched polyurethane.1. reactive functionality is with the monomer synthesis method, the isocyanate group in the synthesis of polyurethane raw material (NCO) and hydroxyl (reactive behavior OH) is very high, can't at room temperature coexist, thereby in preparation HBPU process, need at first synthetic AB
2Monomer (A is NCO usually, and B is OH), and then polycondensation obtains product again.Aryl-aryl carbamate and triazo-compound are used as the blocking group of isocyanate group.Reactive functionality is during with simplex method synthesis of super branched urethane, and because there being inevitably radical protection-go the protection process in synthetic, reactions steps increases, the possibility that also provides side reaction to occur simultaneously, and cost is high, and the application of product does not have competitiveness.Therefore, this synthetic method is studied more in early days, is converted to gradually the more simple and effective synthetic method of seeking relevant super branched polyurethane after the investigators.2. the different monomer synthesis method of reactive functionality in recent years, it is found that with two kinds of monomers that contain respectively A and B functional group and carries out polycondensation, also can prepare hyperbranched polymer, and the method utilization is commercialization monomer cheap and easy to get; Need not radical protection in the reaction process, step is simple, has very large commercial application prospect.
China Patent Publication No. CN1385450A, " super branched polyurethane that the degree of branching is controlled and preparation method thereof " discloses a kind of preparation method of super branched polyurethane, the method is used the vulcabond that will contain two isocyanate groups and is contained the monomer of two amino or hydroxyl and contain an amino and reacts with two or more carboxylic monomers, and by control reaction conditions prepare super branched polyurethane, raw materials used being easy to get, technique is simple.But the method adopts " one kettle way " reinforced, and the degree of branching is controlled, but the molecular conformation of uncontrollable super branched polyurethane.
Germany BASF stock company is CN1791621A in the patent publication No. of China's application, and " producing hyperbranched or super branched polyurethane method " discloses a kind of method of producing hyperbranched or super branched polyurethane.What the method adopted is the same simplex method of reactive functionality, namely synthesizes first the AB with hydroxyl and isocyanate group
2Then the type molecule aggregates into super branched molecule.The method need to be used end-capping reagent, complex process, and side reaction is many.
China Patent Publication No. CN1966544A, " a kind of method for preparing super branched polyurethane " discloses a kind of preparation method of super branched polyurethane.The method vulcabond, oligomer diol, dialkanol ammonia are that raw material prepares super branched polyurethane.The method is utilized A2 type macromonomer and bB
2The type monomer copolymerizable prepares super branched polyurethane, by putting forward the high soft section ratio, obtains the super branched polyurethane of better performances.But doing the every generation branchign of molecule of initial molecule increased number by oligomer diol has much room for improvement.Industrial oligomer diol is a kind of polymkeric substance with certain molecular weight distribution range, has been difficult to pure oligomer diol, so be that the purity of the super branched molecule made of initiator is difficult to guarantee by oligomer diol.Moreover, the technique that this patent adopts is the method with vulcabond and the direct Hybrid Heating of oligomer diol, and the method side reaction is more as can be known by the polycondensation principle, is difficult to obtain the very high hyper-branched polymer of purity.
Summary of the invention
In order to reduce per generation molecule side reaction and side reaction product, improve the purity of super branched polyurethane; Control the form of per generation molecule, improve the molecule regularity; The invention provides a kind of preparation method of new superbrnaching end-hydroxy urethane.
It is initiator that the present invention adopts the very high terminal hydroxy group small molecules polyvalent alcohol low molecular polylol of purity, synthetic a series of superbrnaching end-hydroxies or super branched polyurethane take vulcabond and dioxane hydramine as raw material.Not needing in the building-up process it is characterized in that end-capping reagent, utilize the reactive behavior difference of secondary amine and hydroxyl and isocyanate group and control synthesis of super branched or super branched polyurethane by reaction conditions, reaction conditions is gentle, the mode that adopts the substep that distributes to add is reinforced, product purity high (95～98%).This super branched polyurethane end contains a large amount of hydroxyls, and molecular structure is regular in order.
The concrete preparation manipulation step of superbrnaching end-hydroxy urethane is as follows:
(1) get 3～4 gram terminal hydroxy group small molecules polyvalent alcohols and be dissolved in the 20 gram aprotic organic solvents, obtain terminal hydroxy group small molecules polyhydric alcohol solutions, aprotic organic solvent plays the effect of dissolving small molecules polyvalent alcohol;
(2) get 10～30 gram vulcabond, vulcabond is warmed up to 70～90 ℃, add terminal hydroxy group small molecules polyhydric alcohol solutions, add the catalyzer of 0～0.3% massfraction, reacted 4～6 hours, obtain the hyperbranched prepolymer a of the first-generation
1Isocyanate group in the vulcabond and hydroxyl reaction can obtain the prepolymer that end contains isocyanate groups in the situation that isocyanic ester is excessive.
(3) with the hyperbranched prepolymer a of 20～45 gram first-generation
1Be cooled to 0～15 ℃ with 15～25 gram dioxane hydramine, blend afterreaction 4～6 hours, product just obtains first-generation superbrnaching end-hydroxy urethane A with the vacuum-drying of precipitation agent separating-purifying
1Under 0～15 ℃ of temperature environment, reactivity ratio's isocyanate group of the secondary amine in isocyanate group and the dioxane hydramine and the hydroxyl reaction in the dioxane hydramine are active large, so, the preferential and isocyanic ester radical reaction of the secondary amine in the dioxane hydramine.
The molecular weight of described terminal hydroxy group small molecules polyvalent alcohol is less than 1000g/mol, and each molecule contains two or more hydroxyls; Be specially TriMethylolPropane(TMP), BDO, 1,6-hexylene glycol, neopentyl glycol, ethylene glycol, dipropylene glycol, tetramethylolmethane, glycerine;
Described aprotic organic solvent is the mixture of DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, METHYLPYRROLIDONE, acetone, methyl-sulphoxide, ethyl acetate, methyl-sulphoxide and ethyl acetate;
Described vulcabond is isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (HMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI), 4,4 '-diphenylmethanediisocyanate (MDI);
Described dialkanol amine molecule comprises a secondary amine at least, two hydroxyls; Be specially diethanolamine, diisopropanolamine (DIPA).
Described precipitation agent is acetone, ether, water, Virahol;
Described catalyzer is dibutyl tin laurate, stannous octoate.
The present invention adopts the very high terminal hydroxy group small molecules polyvalent alcohol of purity as initiator, synthetic a series of superbrnaching end-hydroxies or super branched polyurethane take vulcabond and dioxane hydramine as raw material.Do not need end-capping reagent in the building-up process, utilize the reactive behavior difference of secondary amine and hydroxyl and isocyanate group and control synthesis of super branched or super branched polyurethane by reaction conditions, reaction conditions is gentle, the mode that adopts the substep that distributes to add is reinforced, and experimental data shows that the hyper-branched polymer purity that the method obtains can reach more than 95%.This super branched polyurethane end contains a large amount of hydroxyls, and molecular structure is regular in order.The super branched molecule that purity is higher can greatly make things convenient for next step application and theoretical investigation, because the higher super branched molecule of purity can improve the stability of prescription.
The raw materials used wide material sources of superbrnaching end-hydroxy urethane of the present invention's preparation, the building-up process controllability is good, the super branched polyurethane purity of being synthesized is high, compound with regular structure, contain a large amount of terminal hydroxy group, suitable biological medicine carrier, the linking agent done, viscosity modifier, thermosetting material solidifying agent, phase solubilizing agent, auxiliary rheological agents, thixotrope, nucleator etc.
Embodiment
Below in conjunction with embodiment the present invention being further described, is not restriction the present invention.
Embodiment 1:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram TriMethylolPropane(TMP)s (TMP) with 20 gram DMF (DMF) dissolvings, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.Get 19.88 gram isophorone diisocyanates (IPDI) and be heated to 85 ℃, stirring reaction is 6 hours in the adding terminal hydroxy group small molecules polyhydric alcohol solutions, obtains the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 43.88 gram first-generation
1Be cooled to 10 ℃ with 23.5 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 10% aqueous acetone solution separating-purifying final vacuum drying, obtain the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
This first-generation superbrnaching end-hydroxy urethane A
1Purity is higher, and each molecular end contains 6 primary hydroxyls, and steric hindrance is less between the hydroxyl, and reactive behavior is high.This first-generation superbrnaching end-hydroxy urethane A
1Can be applied in urethane synthetic cross-linking agent aspect.
Embodiment 2:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
4 gram TriMethylolPropane(TMP)s (TMP) with 20 gram N,N-dimethylacetamide (DMAC) dissolvings, are obtained terminal hydroxy group small molecules polyhydric alcohol solutions.20.46 gram HMDIs (HMDI) are heated to 90 ℃, and stirring reaction is 4 hours in the adding terminal hydroxy group small molecules polyhydric alcohol solutions, obtains the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 44.46 gram first-generation
1Be cooled to 15 ℃ with 18.5 gram diethanolamine, insulation blending and stirring reaction 6 hours, products therefrom water separating-purifying final vacuum is dry, obtains the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 3:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 3 gram BDOs (BDO) with 20 gram DMF (DMF) dissolvings, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.11.78 gram isophorone diisocyanates (IPDI) are heated to 80 ℃, added terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 34.78 gram first-generation
1Be cooled to 10 ℃ with 17 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 5% ether solution separating-purifying final vacuum drying, obtain the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 4:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram 1,6-hexylene glycols (1,6-HDO) dissolve with 20 gram N-Methyl pyrrolidone (NMP), obtain terminal hydroxy group small molecules polyhydric alcohol solutions.12.02 gram isophorone diisocyanates (IPDI) are heated to 85 ℃ added in the terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 36.02 gram first-generation
1Be cooled to 10 ℃ with 15 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 5% ether solution separating-purifying final vacuum drying, obtain the semi-solid first-generation superbrnaching end-hydroxy of water white transparency urethane A
1
Embodiment 5:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram neopentyl glycol (NEO) with 20 gram acetone solutions, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.13.05 gram isophorone diisocyanates (IPDI) are heated to 90 ℃, add 0.06 gram stannous octoate, add terminal hydroxy group small molecules polyhydric alcohol solutions solution stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 37.5 gram first-generation
1Be cooled to 10 ℃ with 20 gram diisopropanolamine (DIPA), insulation blending reaction 6 hours, products therefrom massfraction are 6% ether solution separating-purifying final vacuum drying, obtain the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
This first-generation superbrnaching end-hydroxy urethane A
1Contain more short-chain branch, see the said structure formula.Can significantly improve the second-order transition temperature of polymkeric substance with its synthesising macromolecule copolymer.
Embodiment 6:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram dipropylene glycol (DPG) with 20 gram methyl-sulphoxide (DMSO) dilutions, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.15.85 gram isophorone diisocyanates (IPDI) are heated to 85 ℃, added terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 39.85 gram first-generation
1Be cooled to 10 ℃ with 16 gram diethanolamine, insulation blending reaction 6 hours, products therefrom water separating-purifying final vacuum is dry, obtains the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 7:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 3 gram tetramethylolmethanes (PER) with 20 gram DMF (DMF) dissolvings, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.11.67 gram isophorone diisocyanates (IPDI) are heated to 90 ℃, added terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 34.67 gram first-generation
1Be cooled to 10 ℃ with 20 gram diethanolamine, insulation blending reaction 6 hours, products therefrom water separating-purifying final vacuum is dry, obtains the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 8:
First-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram TriMethylolPropane(TMP)s (TMP) with 20 gram acetic acid ethyl dissolutions, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.Get 11.58 gram toluene diisocyanates (TDI) and be heated to 70 ℃, added terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 35.58 gram first-generation
1Be cooled to 0 ℃ with 22 gram diethanolamine, insulation blending reaction 4 hours, products therefrom massfraction are 3% isopropanol water solution separating-purifying final vacuum drying, obtain the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 9:
Superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 4 gram TriMethylolPropane(TMP)s (TMP) with the mixed solvent dissolving of 15 gram ethyl acetate and 5 gram methyl-sulphoxides, obtain terminal hydroxy group small molecules polyhydric alcohol solutions.Get 12 gram hexamethylene diisocyanates (HDI) and be heated to 90 ℃, add 0.06 gram dibutyl tin laurate, added terminal hydroxy group small molecules polyhydric alcohol solutions stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the first-generation
1With the hyperbranched prepolymer a of the 36 gram first-generation
1Be cooled to 10 ℃ with 15.03 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 6% ether solution separating-purifying final vacuum drying, obtain the first-generation superbrnaching end-hydroxy urethane A of water white transparency solid
1
Embodiment 10:
First-generation superbrnaching end-hydroxy urethane A with embodiment 1 gained
1Then increase reaction algebraically.
S-generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 10 gram first-generation superbrnaching end-hydroxy urethane A
1With 20 gram DMF (DMF) dissolvings, obtain first-generation superbrnaching end-hydroxy polyurethane solution.Get 12 gram isophorone diisocyanates (IPDI) and be heated to 85 ℃, added first-generation superbrnaching end-hydroxy polyurethane solution stirring reaction 6 hours, obtain the hyperbranched prepolymer a of the s-generation
2With the hyperbranched prepolymer a of the s-generation
2Be cooled to 10 ℃ with 20.5 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 10% aqueous acetone solution separating-purifying final vacuum drying, obtain water white transparency solid A
2, A
2Be exactly s-generation superbrnaching end-hydroxy urethane.
Third generation superbrnaching end-hydroxy urethane target molecular structure formula is as follows:
The synthetic operation step is as follows:
Get 10 gram s-generation superbrnaching end-hydroxy urethane A
2With 20 gram DMF (DMF) dissolvings, obtain s-generation superbrnaching end-hydroxy polyurethane solution.Get 8.65 gram isophorone diisocyanates (IPDI) and be heated to 85 ℃, add s-generation superbrnaching end-hydroxy polyurethane solution, stirring reaction 6 hours obtains the hyperbranched prepolymer a of the third generation
3With the hyperbranched prepolymer a of the third generation
3Be cooled to 10 ℃ with 12.28 gram diethanolamine, insulation blending reaction 6 hours, products therefrom massfraction are 10% aqueous acetone solution separating-purifying final vacuum drying, obtain water white transparency solid A
3, A
3Be exactly third generation superbrnaching end-hydroxy urethane.
The 4th generation superbrnaching end-hydroxy urethane target molecular structure formula as follows:
The synthetic operation step is as follows:
Get 10 gram third generation superbrnaching end-hydroxy urethane A
3With 20 gram DMF (DMF) dissolvings, obtain third generation superbrnaching end-hydroxy polyurethane solution.20.2 gram isophorone diisocyanates (IPDI) are heated to 90 ℃, add A
3DMF solution stirring reaction 6 hours, obtain hyperbranched prepolymer a of the 4th generation
4With hyperbranched prepolymer a of the 4th generation
4Be cooled to 10 ℃ with 25.2 gram diethanolamine, insulation blending reaction 6 hours, products therefrom water separating-purifying final vacuum is dry, obtains water white transparency solid A
4, A
4Be exactly the 4th generation superbrnaching end-hydroxy urethane.
The 4th generation superbrnaching end-hydroxy urethane end contain a large amount of hydroxyls, the rigidity of molecular structure own is larger.This molecule can be used in pharmaceutical carrier, the polymeric rheology auxiliary agent, and polymer curing agents, the aspects such as linking agent have preferably application prospect.
Claims (1)
1. the preparation method of a superbrnaching end-hydroxy urethane is characterized in that comprising following operation steps:
(1) gets 3～4 gram terminal hydroxy group small molecules polyvalent alcohols and be dissolved in the 20 gram aprotic organic solvents, obtain terminal hydroxy group small molecules polyhydric alcohol solutions;
(2) get 10～30 gram vulcabond, vulcabond is warmed up to 70～90 ℃, add terminal hydroxy group small molecules polyhydric alcohol solutions, add the catalyzer of 0～0.3% massfraction, reacted 4～6 hours, obtain the hyperbranched prepolymer a of the first-generation
1
(3) with the hyperbranched prepolymer a of 30～45 gram first-generation
1Be cooled to 0～15 ℃ with 15～25 gram dioxane hydramine, insulation blend afterreaction 4～6 hours, product just obtains first-generation superbrnaching end-hydroxy urethane A with the vacuum-drying of precipitation agent separating-purifying
1
The molecular weight of described terminal hydroxy group small molecules polyvalent alcohol is less than 1000g/mol, and each molecule contains two or more hydroxyls; Be specially TriMethylolPropane(TMP), BDO, 1,6-hexylene glycol, neopentyl glycol, ethylene glycol, dipropylene glycol, tetramethylolmethane, glycerine;
Described aprotic organic solvent is the mixture of DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, METHYLPYRROLIDONE, acetone, methyl-sulphoxide, ethyl acetate, methyl-sulphoxide and ethyl acetate;
Described vulcabond is isophorone diisocyanate (IPDI), 4,4 '-dicyclohexyl methane diisocyanate (HMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), Methylcyclohexyl diisocyanate (HTDI), 4,4 '-diphenylmethanediisocyanate (MDI);
Described dialkanol amine molecule comprises a secondary amine at least, two hydroxyls; Comprise: diethanolamine, diisopropanolamine (DIPA);
Described precipitation agent is acetone, ether, water, Virahol;
Described catalyzer is dibutyl tin laurate, stannous octoate.
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