CN1232558C - Branching degree controllable ultrabranching polyurethane and preparation process thereof - Google Patents
Branching degree controllable ultrabranching polyurethane and preparation process thereof Download PDFInfo
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- CN1232558C CN1232558C CN 02111579 CN02111579A CN1232558C CN 1232558 C CN1232558 C CN 1232558C CN 02111579 CN02111579 CN 02111579 CN 02111579 A CN02111579 A CN 02111579A CN 1232558 C CN1232558 C CN 1232558C
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Abstract
The present invention provides branching degree controllable ultra-branching polyurethane and a preparation process thereof. The preparation process comprises the procedures that (a) diisocyanate containing two isocyanate groups, a monomer containing two amino groups or hydroxy groups, and a monomer containing an amino group and two or more than two hydroxy groups react with a used solvent of a non-protonic solvent at the reaction temperature of minus 100 DEG C to 50 DEG C and the reaction time of 1 minute to 10 days; (b) a mixture obtained at the procedure (a) is heated to 20 DEG C to 150 DEG C to continue to react for 5 minutes to 80 days. The process has the advantages of wide raw material sources, low price, simple and convenient polymerization process, no gelatin and good maneuverability. A polymer with high molecular weight (larger than 100000) and an oligomer can be obtained by changing a molar ratio of the monomers. Polyurea-ammonia ester with different branching degree, thermal performance and mechanical performance can be obtained by changing a charging molar ratio of a C2 or B2 monomer and a CBn monomer. The polymer contains a large number of terminal hydroxyl groups and good solubility, is suitable for being used as effective coating, a rheologic processing additive, a biologic medicine material, a foam plastic, an elastic body, a crosslinking agent, etc. and has wide application prospects.
Description
Technical field:
The present invention relates to super branched polyurethane, particularly controlled super branched polyurethane of the degree of branching and preparation method thereof.
Background technology:
Hyperbranched polymer causes the randomness of its structure owing to the randomness of its synthetic time reaction.Since the laboratory was synthesized report, the polymer science worker who hankers after this respect research was pursuing two important goals always from first kind of hyperbranched polymer: the one, synthesize low price, and have the highly-branched polymers of application potential; The 2nd, the controllability of realization highly-branched polymers structure.Macromol.Rapid Commun., Vol.21,557 (2000) have reported the novel method with cationic ring-opening polymerization synthesis of super branched polyethers, by changing catalyzer (BF
3OEt
3) recently control the degree of crystallinity and the degree of branching of product with feeding in raw material of monomer (3-methyl-3-oxa-methyl alcohol), thus the degree of crystallinity polymkeric substance different obtained with the degree of branching.J.Polym.Sci., Part A:Polym.Chem., Vol.36,955 (1998) have synthesized hyperbranched polymer with the 4-1-chloro-4-methyl-benzene by " from condensation vinyl polymerization method ", when catalyzer and monomer molar are smaller, obtain line polymer; And when catalyzer and monomer molar are bigger, then obtain hyperbranched polymer.Macromolecules; Vol.31; 2381 (1998) synthesis modifications by trivinyl silane improve the degree of branching of hyperbranched polymer; in building-up reactions; with B group protected Abm type monomer and hyperbranched polymer reaction; with b group deprotection, approach 1 hyperbranched polymer again and obtain the degree of branching.The essence of this method is to use AB
xThe type monomer makes linear unit become terminal units gained hyperbranched polymer end-blocking, thereby reaches the purpose that improves the degree of branching.
Urethane is a class has extensive use at numerous areas such as plastics, rubber, fiber, coating, elastomericss polymkeric substance.Because the characteristic of isocyanate groups makes and uses AB
nIt almost is impossible that the type monomer comes synthesis of super branched urethane.
Summary of the invention:
The objective of the invention is to pass through molecular designing, the ingenious differential responses activity of utilizing between different functional groups, with commercial diisocyanate monomer and diamino monomer and mono amino poly-hydroxy monomer direct reaction, synthetic hyperbranched polymer with wide application prospect.So not only can reduce synthesis step, simplify production technique, reduce cost greatly, satisfy the needs of scale operation, and can be by diamino monomer and the monomeric reinforced degree of branching, thermal characteristics and the mechanical property of recently controlling product of mono amino poly-hydroxy.
Content of the present invention is with commercial vulcabond and contains diamino monomer and mono amino poly-hydroxy monomer reaction, synthesized the branched polyurethanes of a series of urea structure uint containings.It is characterized in that constituting in the repeated structural unit of this material and contain urea structure uint (NHCONH) and carbamate structural unit (NHCOO), and mainly form by linear unit, branching unit and terminal units.The linear unit of indication of the present invention comprises the unit that the amino reaction of two in vulcabond and the diamino monomer generates, the amino in vulcabond and the mono amino poly-hydroxy monomer and the unit of a hydroxyl reaction generation and the unit that two hydroxyl reactions in vulcabond and the mono amino poly-hydroxy monomer generate, branching unit comprises the unit that unit that a amino in vulcabond and the mono amino poly-hydroxy monomer and two or more hydroxyl reaction generate and the hydroxyl reaction more than three or three in vulcabond and the mono amino poly-hydroxy monomer generate, terminal units comprise vulcabond only with mono amino poly-hydroxy monomer in the unit of an amino reaction generation, vulcabond only with mono amino poly-hydroxy monomer in the unit that generates of a hydroxyl reaction and vulcabond only with the diamino monomer in-unit that individual amino reaction generates.
The degree of branching of product can be calculated with following formula:
Degree of branching %=(branching unit+terminal units)/(branching unit+terminal units+linear unit) * 100%
Concrete synthetic method of the present invention is: the first step, diisocyanate monomer and diamino monomer and mono amino poly-hydroxy monomer are under-100～50 ℃ of temperature, with diisocyanate monomer and diamino and mono amino poly-hydroxy two monomeric mol ratios is 1/2～2/1, diamino monomer and the monomeric mol ratio of mono amino poly-hydroxy are 1/50～50/1 reinforced proportioning, at aprotic solvent or contain 30 minutes to the 3 day time of reaction in the mixed solvent of aprotic solvent; Second step was warming up to 20～150 ℃ with the first step gained mixture, continued reaction 30 minutes to 10 days.In precipitation agent, precipitate, after filtration, separation, drying, obtain subject polymer.
The diisocyanate monomer that the present invention adopts contains two isocyanate groups (compound N=C=O) or their mixture for all, comprising isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), 4,4 '-ditan-vulcabond (MDI), hexamethylene diisocyanate (HDI), fourth vulcabond (BDI), hot vulcabond (ODI), the last of the ten Heavenly stems vulcabond, naphthalene diisocyanate (NDI), and homologue, derivative and isomer.
The diamino monomer that the present invention adopts is compound or their mixture, particularly piperazine that contains two amino, methylpiperazine, 4,4 '-two piperidines, quadrol, propylene diamine, butanediamine, hexanediamine, octamethylenediamine, decamethylene diamine, carbon 12 amine, carbon 14 amine, carbon 16 amine, carbon 18 amine, carbon 20 amine, and homologue, derivative and isomer.
The mono amino poly-hydroxy monomer that the present invention adopts is for to contain an amino (secondary amino group or primary amino) and the compound of two or two above hydroxyls or their mixture, comprising diethanolamine, and diisopropanolamine (DIPA), 2-amido-2-ethyl-1, ammediol, 1-amido-Pehanorm, N-methyl D-glucosamine, Desoxyadenosine, pancreatic desoxyribonuclease, Deoxyribose cytidine, adenosine, guanosine, cytidine, 2-amino-4,6-dihydroxyl-5-methylpyrimidine, 2-amino-4,6-dihydroxyl-5-pyrimidine, 3-[(1,1-dimethyl-2-hydroxyethyl) amino]-the 2-hydroxy-propanesulfonic acid, GalN, and homologue, derivative and isomer.
By changing diamino monomer and the monomeric reinforced mol ratio of mono amino poly-hydroxy, can obtain the urethane of the degree of branching, thermal characteristics, urea structure uint containing that mechanical property is different.
The present invention's dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate, tetracol phenixin aprotic solvent or the mixed solvent that contains these aprotic solvent are reaction medium.
The present invention is a catalyzer with butyl (tetra) titanate, lauric acid butyl tin, sodium alkoxide, potassium alcoholate, sodium amide, potassium amide, butyllithium, zinc acetate perhaps without catalyzer.
The present invention's acetone, water, ether, methyl alcohol and composition thereof are as precipitation agent.
The structure of polymkeric substance is confirmed through infrared spectra and nuclear magnetic resonance spectroscopy.Molecular weight is measured with GPC, is solvent with DMF.
The branched polyurethanes of novel urea structure uint containing produced according to the present invention and carbamate structural unit (NHCOO).Raw material sources are extensive, and cost of material is cheap, simple synthetic method, and technology is simple, and controllability is good, and the degree of branching, thermal characteristics, mechanical property can be controlled by feed molar ratio, and the product solvability is good, and production cost is low.Polymkeric substance contains a large amount of terminal hydroxy group, and solubility is good, suits to do efficient coating, rheology processing additives, biological medicine material, porous plastics, elastomerics, linking agent etc., has a wide range of applications.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with 1.0514g diethanolamine (10mmol), 0.8614g piperazine (10mmol) is dissolved in 30mLN, in the N-N,N-DIMETHYLACETAMIDE, stirs adding 4.4458g IPDI (20mmol) down, with the sealing of turned welt soft rubber ball, fills N
25-10min.In ice-water-bath, react 5h, be warming up to 60-80 ℃ of reaction 120h.Stopped reaction is used the 600mL acetone precipitation, through suction filtration, washing, vacuum-drying, gets white powder solid 5.79g (91%).Molecular weight of product is 85,700.
Embodiment 2: with 1.2114g 1-amino-orthoformic acid (10mmol), and 0.8614g piperazine (10mmol), 5.0052g MDI (20mmol), 50mLN, the N-N,N-DIMETHYLACETAMIDE adds in the reaction flask of 100mL clean dried, fills N
2, with the sealing of turned welt soft rubber ball, in ice-water-bath, react 5h, be warming up to 60-80 ℃ of reaction 120h.Use the 600mL acetone precipitation,, get white powder solid 6.58g (93%) through suction filtration, washing, vacuum-drying.Molecular weight of product is 72,400.
Claims (8)
1. the preparation method of the controlled super branched polyurethane of the degree of branching, it is characterized in that reacting by following two steps and undertaken: the first step, diisocyanate monomer and diamino monomer and mono amino poly-hydroxy monomer are under-100～50 ℃ of temperature, with diisocyanate monomer and diamino and mono amino poly-hydroxy two monomeric mol ratios is 1/2～2/1, diamino monomer and the monomeric mol ratio of mono amino poly-hydroxy are 1/50～50/1 reinforced proportioning, at aprotic solvent or contain 30 minutes to the 3 day time of reaction in the mixed solvent of aprotic solvent; Second step was warming up to 20～150 ℃ with the first step gained mixture, continued reaction 30 minutes to 10 days.In precipitation agent, precipitate, after filtration, separation, drying, obtain subject polymer.
2. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled, it is characterized in that used diisocyanate monomer is to contain the compound of two isocyanate groups or their mixture, comprising isophorone diisocyanate, tolylene diisocyanate, 4,4 '-ditan-vulcabond, hexamethylene diisocyanate, the fourth vulcabond, hot vulcabond, the last of the ten Heavenly stems vulcabond or naphthalene diisocyanate.
3. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled, it is characterized in that used mono amino poly-hydroxy monomer is to contain the compound of amino and two or two above hydroxyls or their mixture, comprising diethanolamine, diisopropanolamine (DIPA), 2-amido-2-ethyl-1, ammediol, 1-amido-Pehanorm, N-methyl D-glucosamine, Desoxyadenosine, pancreatic desoxyribonuclease, Deoxyribose cytidine, adenosine, guanosine, cytidine, 2-amino-4,6-dihydroxyl-5-methylpyrimidine, 2-amino-4,6-dihydroxyl-5-pyrimidine, 3-[(1,1-dimethyl-2-hydroxyethyl) amino]-2-hydroxy-propanesulfonic acid or GalN.
4. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled is characterized in that used diamino monomer is to contain the compound of two amino or their mixture, comprising piperazine, methylpiperazine, 4,4 '-two piperidines, quadrol, propylene diamine, butanediamine, hexanediamine, octamethylenediamine, decamethylene diamine, carbon 12 amine, carbon 14 amine, carbon 16 amine, carbon 18 amine or carbon 20 amine.
5. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled, it is characterized in that aprotic solvent has dimethyl sulfoxide (DMSO), N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, tetramethylene sulfone, chloroform, tetrahydrofuran (THF), ethyl acetate or tetracol phenixin or contain the mixed solvent of these aprotic solvent.
6. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled is characterized in that without catalyzer, is catalyzer with butyl (tetra) titanate, lauric acid butyl tin, sodium alkoxide, potassium alcoholate, sodium amide, potassium amide, butyllithium or zinc acetate perhaps.
7. the preparation method of the super branched polyurethane that the degree of branching according to claim 1 is controlled is characterized in that with acetone, water, ether or methyl alcohol and composition thereof as precipitation agent.
8. the controlled super branched polyurethane of the degree of branching, it is characterized in that adopting the controlled super branched polyurethane of the degree of branching of the described preparation method's acquisition of claim 1～7, contain urea structure uint and carbamate structural unit in the repeated structural unit of this polymkeric substance, polymkeric substance is mainly by linear unit, branching unit and terminal units are formed, linear unit comprises the unit that the amino reaction of two in vulcabond and the diamino monomer generates, the amino in vulcabond and the mono amino poly-hydroxy monomer and the unit of a hydroxyl reaction generation and the unit that two hydroxyl reactions in vulcabond and the mono amino poly-hydroxy monomer generate, branching unit comprises the unit that unit that a amino in vulcabond and the mono amino poly-hydroxy monomer and two or more hydroxyl reaction generate and the hydroxyl reaction more than three or three in vulcabond and the mono amino poly-hydroxy monomer generate, terminal units comprise vulcabond only with mono amino poly-hydroxy monomer in the unit of an amino reaction generation, vulcabond only with mono amino poly-hydroxy monomer in the unit that generates of a hydroxyl reaction and vulcabond only with the diamino monomer in a unit that amino reaction generates.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10322401A1 (en) * | 2003-05-16 | 2004-12-02 | Basf Ag | Process for the production of dendrimeric or hyperbranched polyurethanes |
| CN101445697B (en) * | 2008-11-26 | 2011-03-23 | 陕西科技大学 | Hyper branched polyurethane leather coating agent and preparation method thereof |
| CN102942664A (en) * | 2012-11-28 | 2013-02-27 | 安徽大学 | Preparation method of hydroxyl-terminated hyperbranched polyurethane |
| CN104356338B (en) * | 2014-10-30 | 2016-10-05 | 华南理工大学 | A kind of selfreparing polyurethane coating and preparation method thereof |
| CN105669929A (en) * | 2016-03-21 | 2016-06-15 | 美瑞新材料股份有限公司 | Engineering thermoplastic polyurethane elastomer and preparation method thereof |
| WO2017214745A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Process for preparing hyperbranched polyurethane |
| CN108039244B (en) * | 2017-12-29 | 2019-05-31 | 东莞市中亚电缆有限公司 | A kind of cable insulation external application water blocking filler and manufacturing method |
| CN108864407B (en) * | 2018-08-02 | 2020-12-22 | 北京中纺化工股份有限公司 | Washing-resistant water-repellent synergist and preparation method and application thereof |
| CN115232318B (en) * | 2022-08-24 | 2023-12-26 | 宁波锋成先进能源材料研究院有限公司 | A kind of nonionic polymer surfactant and its preparation method and application |
| CN116675858B (en) * | 2023-07-19 | 2025-08-29 | 扬州市祥华新材料科技有限公司 | Preparation method of amino-terminated hyperbranched polysulfide and internally cross-linked modified polyurethane prepared therefrom |
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