CN105778029B - A kind of preparation method of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane - Google Patents
A kind of preparation method of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane Download PDFInfo
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- CN105778029B CN105778029B CN201610149715.2A CN201610149715A CN105778029B CN 105778029 B CN105778029 B CN 105778029B CN 201610149715 A CN201610149715 A CN 201610149715A CN 105778029 B CN105778029 B CN 105778029B
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The present invention is a kind of preparation method of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane, and preparation method is: preparing AB by Michael addition reaction with methyl acrylate (MA) and diethanol amine (DEA) first2Then monomer makes AB2Monomer is grafted on three-(2- ethoxy) isocyanuric acid esters (THEIC), it is poly- (isocyanuric acid ester -ester) (HPICE) that superbrnaching end-hydroxy is prepared, pass through graft reaction finally by HPICE and the Waterborne Polyurethane Prepolymer of preparation, it is neutralized at salt, hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane with nucleocapsid structure is prepared in emulsion dispersion；The present invention realizes a kind of preparation of new structural hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to arrives a kind of hyperbranched poly (isocyanuric acid ester -ester) type
Aqueous polyurethane preparation method.
Background technique
Aqueous polyurethane (WPU) refers to the polyurethane particles binary colloidal system being dispersed in continuous phase (water), has not
Easy firing, low-carbon environment-friendly, it is safe and reliable the advantages that and by the concern of researcher.The product made of polyurethane resin is wide
It is general to be applied to the industries such as coating, adhesive, plastics, building, it is a kind of functional polymer material being widely used.Aqueous poly- ammonia
Although ester has many excellent performances, there is also all various deficiencies, such as chain molecule of most of aqueous polyurethanes
Linear structure, the poor water resistance of film, poor heat resistance, solid content are low, hardness is low etc..
Hyperbranched Polymer with Terminal Hydroxyl is a kind of novel high polymer material, not only has the unique cavity of dissaving polymer
Structure and branching unit have chemical reactivity very high simultaneously because a large amount of hydroxyl is contained in structure outer end, and dissolubility is good,
The advantages that rheological characteristic is good.Due to the unformed and low viscosity of Hyperbranched Polymer with Terminal Hydroxyl structure make reaction can smoothly into
Row is protected so Hyperbranched Polymer with Terminal Hydroxyl is also a kind of intermediate of high molecular material of synthesis well in agricultural, environment
Shield, life science, medical carrier, catalyst etc. have a wide range of applications and important value.Therefore terminal hydroxy group is surpassed
Branched polymer is applied in Water-based polyurethane elastomer, it is made to have both the architectural characteristic of dissaving polymer and aqueous poly- ammonia
The excellent properties of ester, to meet the needs of market is to multifunction aqueous polyurethane.
Summary of the invention
In order to overcome the defects of the prior art described above, the purpose of the present invention is to provide a kind of hyperbranched poly (isocyanuric acids
Ester -ester) type aqueous polyurethane preparation method.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method, comprising:
Step 1: the synthesis of superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester): first that diethanol amine (DEA) is completely molten
Then solution adds methyl acrylate (MA) in anhydrous methanol, colorless viscous liquid is prepared by Michael addition reaction
Body AB2Monomer, i.e. N, N- dihydroxy ethyl -3- amidos propionic acid methyl esters；By the AB after purification2Monomer dropping is to N, N- dimethyl formyl
In three-(2- ethoxy) isocyanuric acid esters (THEIC) of amine dissolution, catalyst is added, terminal hydroxy group is obtained by ester exchange reaction
Hyperbranched poly (isocyanuric acid ester -ester) (HPICE)；
Step 2: the synthesis of Waterborne Polyurethane Prepolymer: diisocyanate is mixed with oligomer dihydric alcohol, adds and contains
The dihydric alcohol and small molecule chain extender of hydrophilic radical, finally carry out isocyanate group with dehydrated alcohol partially end-blocked, obtain water
Property base polyurethane prepolymer for use as；
Step 3: the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane: the HPICE that step 1 is obtained
It is dissolved in solvent, the Waterborne Polyurethane Prepolymer obtained with step 2 carries out graft reaction, neutralizes finally by salt forming agent, cream
Change dispersion and hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane with nucleocapsid structure is prepared.
The reaction condition of the synthesis of terminal hydroxy group hyperbranched poly (isocyanuric acid ester -ester) in the step one are as follows: diethanol
Amine (DEA) obtains AB in 30 DEG C~40 DEG C 3~5h of reaction for 1 ︰, 1.05~1 ︰ 2.0 with methyl acrylate (MA) molar ratio2It is single
The crude product of body；Again by crude product through vacuum filter, ether washing is to get the AB to after purifying2Monomer；Finally by 28.65~
30.0g AB2Three-(2- ethoxy) isocyanuric acid esters that the N,N-dimethylformamide of monomer dropping to 2~10g dissolve
(THEIC) in, catalyst amount AB2The 1%~5% of the quality summation of monomer and THEIC, is held by ester exchange reaction
Hydroxyl hyperbranched poly (isocyanuric acid ester -ester) (HPICE)；
As n (AB2): poly- (isocyanuric acid ester -ester) G of generation superbrnaching end-hydroxy can be obtained when being 3 ︰ 1 in n (THEIC)1
(OH)6, reaction temperature is 90 DEG C~140 DEG C, and the time is 1~6h；
Using the generation product of synthesis as core, with AB2Monomer is poly- according to the superbrnaching end-hydroxy that 6 ︰, 1 molar ratio obtained for two generations
(isocyanuric acid ester -ester) crude product；It is through vacuum filter, acetone solution, methylene chloride reprecipitation, ether washing by crude product again
The superbrnaching end-hydroxy for obtaining yellow is poly- (isocyanuric acid ester -ester) (HPICE)；
Using two generation products of synthesis as core, with AB2Monomer obtains the superbrnaching end-hydroxy of three generations according to 12 ︰, 1 molar ratio
Poly- (isocyanuric acid ester -ester) crude product；Crude product is washed through vacuum filter, acetone solution, methylene chloride reprecipitation, ether again
The superbrnaching end-hydroxy for obtaining yellow is poly- (isocyanuric acid ester -ester) (HPICE).
Mixing diisocyanate with oligomer dihydric alcohol in the step two, diisocyanate and oligomer binary
The molar ratio of alcohol is (2.5~6): 1, in 70~90 DEG C of 1~3h of reaction, add 3.0%~6.0% binary containing hydrophilic radical
Alcohol (on the basis of gross mass of the diisocyanate with oligomer dihydric alcohol) and 1.0%~1.8% small molecule chain extender are (different with two
On the basis of the gross mass of cyanate and oligomer dihydric alcohol), in 75~90 DEG C of 2~3h of reaction, it is eventually adding 0.5%~2.5%
Dehydrated alcohol (on the basis of the gross mass of diisocyanate and oligomer dihydric alcohol) part envelope is carried out to diisocyanate ester group
End reaction, in 60~80 DEG C of 0.5~3.0h of reaction, obtains Waterborne Polyurethane Prepolymer.
The synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane in the step three: will be in step 1
Obtained HPICE is dissolved in solvent, reacts 2~6h in 40~90 DEG C with the Waterborne Polyurethane Prepolymer that step 2 obtains, control
NCO/OH molar ratio is 1.2~1.7 in reaction system processed；It is neutralized finally by salt forming agent, emulsion dispersion is prepared with core-
Hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane of shell structure.
Catalyst in the step one is in p-methyl benzenesulfonic acid, phosphoric acid, the concentrated sulfuric acid, concentrated hydrochloric acid or tetrabutyl titanate
It is a kind of.
Solvent in the step three is the mixed solvent of one or both of acetone, DMF and DMAc kind.
The salt forming agent is one of triethylamine, ammonium hydroxide, sodium hydroxide or mixture, and wherein salt forming agent accounts for aqueous poly-
The 90%~100% of the amount of carboxyl total material in urethane performed polymer.
Diisocyanate in the step two is 4,4`- methyl diphenylene diisocyanate (MDI), oneself is two different by 1,6-
One of cyanate (HDI), isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) or a variety of mixing
Object.
Oligomer dihydric alcohol in the step two is polytetrahydrofuran (PTMG), polypropylene glycol (PPG), polyethylene glycol
(PEG), polyethylene glycol adipate glycol (PEA), polycaprolactone glycol (PCL), polyadipate 1,4-butanediol ester (PBA),
One of polycarbonate glycol (PCDL) or a variety of mixtures.
The dihydric alcohol containing hydrophilic radical in the step two is dihydromethyl propionic acid (DMPA), dimethylolpropionic acid
(DMBA), one of N, N- dihydroxy list maleamic acid, tartaric acid or a variety of mixtures.
Small molecule chain extender in the step two is 1,4- butanediol (BDO), 1,6-HD, glycerol, three hydroxyl first
One in base propane (TMP), diethylene glycol (DEG) (DEG), triethylene glycol, neopentyl glycol (NPG), sorbierite or diethylaminoethanol (DEAE)
Kind or a variety of mixtures.
Superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester) in the step one is used for the expansion of Waterborne Polyurethane Prepolymer
In the chain stage, NCO/OH molar ratio is 1.2~1.7 in reaction system processed, and the hyperbranched poly (isocyanide of different molecular quality can be made
Urea acid esters -ester) type aqueous polyurethane.
Beneficial effects of the present invention: the present invention can need to prepare the poly- (isocyanide of serial superbrnaching end-hydroxy according to application
Urea acid esters -ester): poly- (isocyanuric acid ester -ester) G of generation superbrnaching end-hydroxy1(OH)6, poly- (the isocyanide urea of two generation superbrnaching end-hydroxies
Acid esters -ester) G2(OH)12, poly- (isocyanuric acid ester -ester) G of three generations's superbrnaching end-hydroxy3(OH)24, etc., wherein superbrnaching end-hydroxy
Three-(2- ethoxy) isocyanuric acid esters (THEIC) in polymer architecture have triazine ring skeleton, and fabulous thermal stability is resistance to
Time property and anti-flammability, three hydroxyls are through AB2Branched structure can be formed after monomer modified, make its structure with more stability, institute
Its comprehensive performance can be improved to be applied in aqueous polyurethane.The series of products have a good application prospect.
Detailed description of the invention
Fig. 1 is the synthesis of superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester).
Fig. 2 is partially enclosed Waterborne Polyurethane Prepolymer.
Fig. 3 is the graft reaction of Waterborne Polyurethane Prepolymer and superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester).
Specific embodiment
The present invention is described in further details with embodiment with reference to the accompanying drawing.
Embodiment 1
Step 1: poly- (isocyanuric acid ester -ester) G of superbrnaching end-hydroxy1(OH)6Synthesis:
Diethanol amine (DEA) 0.1mol is weighed to be dissolved completely in the 10mL methanol solution that temperature is room temperature；In room temperature item
Under part, the ratio for being 1 ︰ 2 according to diethanol amine (DEA) and methyl acrylate (MA) molar ratio is added dropwise methyl acrylate (MA), drop
It is warming up to 35 DEG C after adding, stirs lower insulation reaction 3.5h, AB is made2Monomer；By AB obtained2Monomer crude product is through vacuum mistake
Filter and ether extracting and washing obtain AB2Monomer is a kind of colorless and transparent oily object, i.e. N, N- dihydroxy ethyl -3- amidos propionic acid first
Ester；It is catalyst 2% (with AB using p-methyl benzenesulfonic acid2Subject to monomer and THEIC mass summation), by above-mentioned AB2Monomer 28.7g drop
It is added in three-(2- ethoxy) isocyanuric acid ester (THEIC) solution of 5g n,N-Dimethylformamide dissolution, is 115 in temperature
3.0h is reacted under the conditions of DEG C, and the crude product of superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester) (HPAE) is prepared；It will be obtained
Poly- (isocyanuric acid ester -ester) crude product of superbrnaching end-hydroxy is extracted through vacuum filter, acetone solution, methylene chloride reprecipitation, ether
It washs up to poly- (isocyanuric acid ester -ester) G of generation superbrnaching end-hydroxy1(OH)6；
Step 2: the synthesis of Waterborne Polyurethane Prepolymer:
By 40.0g PTMG-2000, the drop of 11.2g IPDI and 3~4 dibutyl tin dilaurate (DBTDL) is added to there-necked flask
In, 2h is reacted at 70 DEG C, is added at 2.0g dihydromethyl propionic acid and 80 DEG C of 0.6g1,4- butanediol (BDO) and is reacted 2~3h, drop
For temperature to 70 DEG C, addition 0.4g dehydrated alcohol is partially end-blocked to isocyanate group, reacts 30min, obtains Waterborne Polyurethane Prepolymer；
Step 3: the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane:
Poly- (isocyanuric acid ester -ester) 0.6g of superbrnaching end-hydroxy obtained in step 1 is dissolved in acetone, with step
It obtains reacting 3h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in two, is cooled to 50 DEG C, 1.5g triethylamine is added and is neutralized,
Deionized water emulsion dispersion is added to obtain hyperbranched poly (isocyanuric acid ester -ester) type under the mixing speed of 1500r/min aqueous poly-
Urethane.
Embodiment 2
By 30.0g PPG-2000, the drop of 12.3g IPDI and 3~4 dibutyl tin dilaurate (DBTDL) is added to there-necked flask
In, react 80min at 70 DEG C, be added reaction 3 at 1.8g dihydromethyl propionic acid and 80 DEG C of 0.5g1,4- butanediol (BDO)~
4h is cooled to 70 DEG C, and addition 0.4g dehydrated alcohol is partially end-blocked to isocyanate group, reacts 30min, it is pre- to obtain aqueous polyurethane
Aggressiveness；
By poly- (isocyanuric acid ester -ester) G of the superbrnaching end-hydroxy in embodiment 11(OH)60.4g is dissolved in acetone, with
It obtains reacting 3h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in step 2, is cooled to 40 DEG C, 1.3g triethylamine is added and carries out
It neutralizes, under the mixing speed of 1500r/min plus deionized water emulsion dispersion obtains hyperbranched poly (isocyanuric acid ester -ester) type water
Property polyurethane.
Embodiment 3
Step 1: poly- (isocyanuric acid ester -ester) G of superbrnaching end-hydroxy2(OH)12Synthesis:
By G obtained in embodiment 11(OH)64.2g and AB2Monomer is catalysis with p-methyl benzenesulfonic acid according to 1 ︰ 6 of molar ratio
Agent 2% is (with AB2Subject to monomer and THEIC mass summation), it is stirred to react 5h at 120 DEG C, obtains 2nd generation superbrnaching end-hydroxy
Poly- (isocyanuric acid ester -ester) crude product G2(OH)12；By poly- (isocyanuric acid ester -ester) G of superbrnaching end-hydroxy obtained2(OH)12Crude product
It is poly- (different that second generation superbrnaching end-hydroxy is obtained through vacuum filter, acetone solution, methylene chloride reprecipitation, ether extracting and washing
Cyanurate -ester) G2(OH)12；
Step 2: the synthesis of Waterborne Polyurethane Prepolymer:
By 40g PPG-2000, the drop of 13.4g IPDI and 3~4 dibutyl tin dilaurate (DBTDL) is added in there-necked flask,
1h is reacted at 85 DEG C, and 2.1g dihydromethyl propionic acid is added and 0.5g 1,4-butanediol (BDO) reacts 2~3h at 80 DEG C, drops
For temperature to 70 DEG C, addition 0.3g dehydrated alcohol is partially end-blocked to isocyanate group, reacts 30min, obtains Waterborne Polyurethane Prepolymer；
Step 3: the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane:
Poly- (isocyanuric acid ester -ester) G of superbrnaching end-hydroxy will be obtained in step 12(OH)121.3g is dissolved in acetone,
With obtain reacting 4h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in step 2, be cooled to 45 DEG C of addition 1.6g triethylamines and carry out
It neutralizes, under the mixing speed of 1500r/min plus deionized water emulsion dispersion obtains hyperbranched poly (isocyanuric acid ester -ester) type water
Property polyurethane.
Embodiment 4
By 30.0g PTMG-2000, the drop of 16.7g IPDI and 3~4 dibutyl tin dilaurate (DBTDL) is added to there-necked flask
In, react 80min at 70 DEG C, be added reaction 3 at 2.2g dihydromethyl propionic acid and 80 DEG C of 0.6g1,4- butanediol (BDO)~
4h is cooled to 70 DEG C, and addition 0.3g dehydrated alcohol is partially end-blocked to isocyanate group, reacts 30min, it is pre- to obtain aqueous polyurethane
Aggressiveness；
By poly- (isocyanuric acid ester -ester) G of the superbrnaching end-hydroxy in embodiment 32(OH)121.5g is dissolved in acetone, with
It obtains reacting 4h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in step 2, is cooled to 40 DEG C, 1.7g triethylamine is added and carries out
It neutralizes, under the mixing speed of 1500r/min plus deionized water emulsion dispersion obtains hyperbranched poly (isocyanuric acid ester -ester) type water
Property polyurethane.
Embodiment 5
Step 1: poly- (isocyanuric acid ester -ester) G of superbrnaching end-hydroxy3(OH)24Synthesis:
By G obtained in embodiment 32(OH)126.9g and AB2Monomer is to urge with p-methyl benzenesulfonic acid according to 1 ︰ 12 of molar ratio
Agent 2% is (with AB2Subject to monomer and match gram mass summation), it is stirred to react 6h at 120 DEG C, obtains the 3rd generation terminal hydroxy group over-expense
Change poly- (isocyanuric acid ester -ester) crude product G3(OH)24.By poly- (isocyanuric acid ester -ester) crude product of superbrnaching end-hydroxy obtained through true
Empty filtering, acetone solution, methylene chloride reprecipitation, ether extracting and washing obtain poly- (the isocyanide urea of third generation superbrnaching end-hydroxy
Acid esters -ester) G3(OH)24；
Step 2: the synthesis of Waterborne Polyurethane Prepolymer:
By 30g polycarbonate glycol (PCDL), 10.5g toluene di-isocyanate(TDI) (TDI), 0.5g1,4- butanediol (BDO)
It is added in there-necked flask with 3~4 drops dibutyl tin dilaurate (DBTDL), 1h is reacted at 85 DEG C, 2.1g dihydroxymethyl third is added
Sour (DMPA) reacts 2.5h at 80 DEG C, is cooled to 70 DEG C, and addition 0.3g dehydrated alcohol is partially end-blocked to isocyanate group, reaction
30min obtains Waterborne Polyurethane Prepolymer；
Step 3: the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane:
By terminal hydroxy group hyperbranched poly in step 1 (isocyanuric acid ester -ester) G3(OH)241.8g is dissolved in DMF, with step
It obtains reacting 5h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in two, 1.6g triethylamine is added and neutralizes, in stirring for 1500r/min
It mixes under speed plus deionized water emulsion dispersion obtains hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane.
Embodiment 6
By 30.0g polycarbonate glycol (PCDL), the drop of 13.1g TDI and 3~4 dibutyl tin dilaurate (DBTDL) adds
Into there-necked flask, 80min is reacted at 70 DEG C, is added at 2.2g dihydromethyl propionic acid and 80 DEG C of 0.6g1,4- butanediol (BDO)
3~4h is reacted, is cooled to 70 DEG C, addition 0.4g dehydrated alcohol is partially end-blocked to isocyanate group, reacts 30min, obtains aqueous
Base polyurethane prepolymer for use as；
By poly- (isocyanuric acid ester -ester) G of the superbrnaching end-hydroxy in embodiment 53(OH)241.5g is dissolved in DMF, with step
It obtains reacting 5h at 80 DEG C of hyperbranched aqueous polyurethane performed polymer in rapid two, is cooled to 40 DEG C, be added in the progress of 1.7g triethylamine
With, under the mixing speed of 1500r/min plus deionized water emulsion dispersion to obtain hyperbranched poly (isocyanuric acid ester -ester) type aqueous
Polyurethane.
In the present invention, the reaction equation related generally to is as follows: wherein schematic structure is only with IPDI, polyetherdiol, two
Hyperbranched poly (isocyanuric acid made from hydroxymethyl propionic acid and hyperbranched poly (isocyanuric acid ester -ester) containing 6 terminal hydroxyls
Ester -ester) type aqueous polyurethane structure, be not limited to using the hyperbranched water of other structures made from other raw materials described in claim
The structure of property polyurethane.
Claims (10)
1. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method characterized by comprising
Step 1: the synthesis of superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester):
Diethanol amine (DEA) is dissolved completely in anhydrous methanol first, methyl acrylate (MA) is then added, passes through mikey
Colourless viscous liquid AB is prepared for addition reaction in you2Monomer, i.e. N, N- dihydroxy ethyl -3- amidos propionic acid methyl esters；After purifying
AB2In three (2- ethoxy) isocyanuric acid esters (THEIC) that monomer dropping is dissolved to n,N-Dimethylformamide, catalysis is added
It is poly- (isocyanuric acid ester -ester) (HPICE) to obtain superbrnaching end-hydroxy by ester exchange reaction for agent；
Step 2: the synthesis of Waterborne Polyurethane Prepolymer:
Diisocyanate is mixed with oligomer dihydric alcohol, adds dihydric alcohol and small molecule chain extender containing hydrophilic radical, most
Isocyanate group is carried out with dehydrated alcohol afterwards partially end-blocked, obtains Waterborne Polyurethane Prepolymer；
Step 3: the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane:
The HPICE that step 1 is obtained is dissolved in solvent, and the Waterborne Polyurethane Prepolymer obtained with step 2 be grafted anti-
It answers, is neutralized finally by salt forming agent, the hyperbranched poly (isocyanuric acid ester -ester) with nucleocapsid structure is prepared in emulsion dispersion
Type aqueous polyurethane.
2. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is, the reaction condition of the synthesis of terminal hydroxy group hyperbranched poly (isocyanuric acid ester -ester) in the step one are as follows: diethanol amine
(DEA) AB is obtained in 30 DEG C~40 DEG C 3~5h of reaction for 1 ︰, 1.05~1 ︰ 2.0 with methyl acrylate (MA) molar ratio2Monomer
Crude product；Again by crude product through vacuum filter, ether washing is to get the AB to after purifying2Monomer；Finally by 28.65~
30.0g AB2Three (2- ethoxy) isocyanuric acid esters that the N,N-dimethylformamide of monomer dropping to 2~10g dissolve
(THEIC) in, catalyst amount AB2The 1%~5% of the quality summation of monomer and THEIC, is held by ester exchange reaction
Hydroxyl hyperbranched poly (isocyanuric acid ester -ester) (HPICE)；
As n (AB2): poly- (isocyanuric acid ester -ester) G of generation superbrnaching end-hydroxy can be obtained when being 3 ︰ 1 in n (THEIC)1(OH)6,
Reaction temperature is 90 DEG C~140 DEG C, and the time is 1~6h；
Using the generation product of synthesis as core, with AB2Monomer obtains the poly- (isocyanide of superbrnaching end-hydroxy in two generations according to 6 ︰, 1 molar ratio
Urea acid esters -ester) crude product；Crude product is obtained through vacuum filter, acetone solution, methylene chloride reprecipitation, ether washing again
The superbrnaching end-hydroxy of yellow is poly- (isocyanuric acid ester -ester) (HPICE)；
Using two generation products of synthesis as core, with AB2Monomer is poly- (different according to the superbrnaching end-hydroxy that 12 ︰, 1 molar ratio obtains three generations
Cyanurate -ester) crude product；Crude product is washed through vacuum filter, acetone solution, methylene chloride reprecipitation, ether again to obtain the final product
Superbrnaching end-hydroxy to yellow is poly- (isocyanuric acid ester -ester) (HPICE).
3. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is, mixing diisocyanate with oligomer dihydric alcohol in the step two, diisocyanate and oligomer binary
The molar ratio of alcohol is (2.5~6): 1, in 70~90 DEG C of 1~3h of reaction, add 3.0%~6.0% binary containing hydrophilic radical
Pure and mild 1.0%~1.8% small molecule chain extender, dihydric alcohol on the basis of the gross mass of diisocyanate and oligomer dihydric alcohol,
Small molecule chain extender is on the basis of the gross mass of diisocyanate and oligomer dihydric alcohol, in 75~90 DEG C of 2~3h of reaction, finally
The dehydrated alcohol for being added 0.5%~2.5% carries out partially end-blocked reaction to diisocyanate ester group, react 0.5 in 60~80 DEG C~
3.0h obtains Waterborne Polyurethane Prepolymer.
4. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is, the synthesis of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane in the step three: will obtain in step 1
To HPICE be dissolved in solvent, react 2~6h in 40~90 DEG C with the Waterborne Polyurethane Prepolymer that step 2 obtains, control
NCO/OH molar ratio is 1.2~1.7 in reaction system；It is neutralized finally by salt forming agent, emulsion dispersion is prepared with core-shell structure copolymer
Hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane of structure.
5. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is that the catalyst in the step one is in p-methyl benzenesulfonic acid, phosphoric acid, the concentrated sulfuric acid, concentrated hydrochloric acid or tetrabutyl titanate
It is a kind of.
6. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is that the solvent in the step three is the mixed solvent of one or both of acetone, DMF and DMAc.
7. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is that the salt forming agent is one of triethylamine, ammonium hydroxide, sodium hydroxide or mixture, and wherein salt forming agent accounts for aqueous poly-
The 90%~100% of the amount of carboxyl total material in urethane performed polymer.
8. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is, the diisocyanate in the step two is 4,4`- methyl diphenylene diisocyanate (MDI), oneself is two different by 1,6-
One of cyanate (HDI), isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) or a variety of mixing
Object.
9. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1, special
Sign is that the oligomer dihydric alcohol in the step two is polytetrahydrofuran (PTMG), polypropylene glycol (PPG), polyethylene glycol
(PEG), polyethylene glycol adipate glycol (PEA), polycaprolactone glycol (PCL), polyadipate 1,4-butanediol ester (PBA),
One of polycarbonate glycol (PCDL) or a variety of mixtures.
10. a kind of hyperbranched poly (isocyanuric acid ester -ester) type aqueous polyurethane preparation method according to claim 1,
It is characterized in that, the dihydric alcohol containing hydrophilic radical in the step two is dihydromethyl propionic acid (DMPA), dimethylolpropionic acid
(DMBA), one of tartaric acid or a variety of mixtures；Small molecule chain extender in the step two is 1,4- butanediol
(BDO), 1,6-HD, glycerol, trimethylolpropane (TMP), diethylene glycol (DEG) (DEG), triethylene glycol, neopentyl glycol (NPG) or mountain
One of pears alcohol or a variety of mixtures；
Superbrnaching end-hydroxy poly- (isocyanuric acid ester -ester) in the step one is used for the chain extension rank of Waterborne Polyurethane Prepolymer
Section, NCO/OH molar ratio is 1.2~1.7 in reaction system, and the hyperbranched poly (isocyanuric acid of different molecular quality can be made
Ester -ester) type aqueous polyurethane.
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| CN107141440B (en) * | 2017-06-16 | 2020-07-28 | 北京化工大学 | Rigid ring modified organosilicon polyurethane acrylate water-based oligomer and preparation method thereof |
| CN110437402A (en) * | 2019-08-09 | 2019-11-12 | 中国科学院兰州化学物理研究所 | A kind of preparation method of the interpenetrating net polymer with shape-memory properties |
| CN110606934A (en) * | 2019-08-14 | 2019-12-24 | 惠东县鞋业科技创新中心 | Environment-friendly water-based anionic polyurethane adhesive and preparation method thereof |
| CN114645465B (en) * | 2020-12-17 | 2024-03-08 | 洛阳尖端技术研究院 | Polyurea elastomer composite material and preparation method thereof |
| CN112608443B (en) * | 2020-12-30 | 2021-11-12 | 江南大学 | Preparation method of heat-resistant flame-retardant UV (ultraviolet) curing waterborne polyurethane |
| CN115124679B (en) * | 2022-07-11 | 2023-09-12 | 陕西科技大学 | Self-repairing hyperbranched waterborne polyurethane and preparation method and application thereof |
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| US20110065886A1 (en) * | 2007-10-12 | 2011-03-17 | Evonik Degussa Gmbh | Process for preparing hyperbranched, dendritic polyurethanes by means of reactive extrusion |
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| US20110065886A1 (en) * | 2007-10-12 | 2011-03-17 | Evonik Degussa Gmbh | Process for preparing hyperbranched, dendritic polyurethanes by means of reactive extrusion |
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