CN106543402A - A kind of preparation method of cross-linking block graft type high molecular polymer - Google Patents
A kind of preparation method of cross-linking block graft type high molecular polymer Download PDFInfo
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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
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- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
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- C08G18/286—Oximes
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
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- C08G18/4804—Two or more polyethers of different physical or chemical nature
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
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Abstract
The invention discloses a kind of preparation method of cross-linking block graft type high molecular polymer.Some current polyurethaness amphiphilic polymers, due to the restriction of its hydrophilic segment and oleophylic segment Space expanding, constrain its extensive application in fields such as emulsion polymerization, pigment dispersions.The present invention is with glyceryl monostearate and polyisocyanates as raw material, react with the polyols blend of trimethylolpropane poly glycol monomethyl ether and other polyhydric alcohol, finally carry out chain extension, end-blocking, emulsifying, distillation etc. and generate a kind of cross-linking block graft type polyurethane family macromolecule polymer.The distinctive block graft type structure of the polymer makes it have preferable surface activity, cooperates with the active group in its structure so as to have preferable application prospect in fields such as pigment dispersing agent, stabilizer and emulsion polymerizations；Simultaneously remain substantial amounts of active group on polymer, during heating can with hydroxyl, amino or itself be crosslinked, can make polymeric film that there is good resistance to water, adhesive force and adhesion strength.
Description
Technical field
The present invention relates to chemical field, specifically a kind of poly- in pigment dispersing agent, stabilizer and emulsion
There is the preparation method of the cross-linking block-graft type polyurethane class high molecular polymer of preferable application prospect in the fields such as conjunction.
Background technology
Aqueous polyurethane (WPU) is the binary colloidal system with water as disperse medium, compared with solvent borne polyurethane, is had
Do not fire, abnormal smells from the patient is little, free from environmental pollution, energy saving, the advantages of operate easy to process, thus increasingly attract much attention,
And progressively applied in fields such as dispersant, emulsion polymerizations.Contain substantial amounts of isocyanates in one side aqueous polyurethane
Base, hydroxyl isoreactivity group, can pass through chemical bond or molecule with the hydroxyl on fabric or dyestuff, amino etc. at a lower temperature
Intermolecular forces are combined, it is possible to increase the dispersion stabilization of system, strengthen the fastness such as washable of polymer；On the other hand in breast
Used in liquid polymerization, water-based polyurethane macromolecule emulsifier can improve resistance to water, adhesive force and the adhesion strength of film, increase
Strong its film property and elasticity.
Chinese patent 201510889084.3 discloses a kind of Y types three block non-ion aqueous polyurethane class surface activity
Agent, it is prepared from by glyceryl monostearate, isocyanates and Polyethylene oxide monomethyl ether.During the patent claims its molecular structure
Methyl structural can effectively reduce the surface tension of solution, and be mainly used in the aspects such as the displacement of reservoir oil, sewage disposal, with green, life
The advantages of thing compatibility is good, it is shorter yet with its hydrophilic segment, limit its answering in fields such as emulsion polymerization, pigment dispersions
With.
Chinese patent 200610100820.3 discloses a kind of preparation method of polyurethane dispersant, and it is by the two of hydrophobic
First alcohol or diamine or naphthols and isocyanates reacting by heating, after solvent dilution, add Polyethylene Glycol or polyethyleneglycol first
Ether is obtained with the mixture reaction of catalyst.The patent claims the dispersant to have makes granules of pigments be uniformly dispersed and good stability etc.
Advantage, but due to its overall structure be straight chain, hydrophilic segment formed hydrated sheath external interference resistance it is weaker.
The content of the invention
The technical problem to be solved is the defect for overcoming above-mentioned prior art to exist, there is provided a kind of cross-linking embedding
The preparation method of section-graft type polyurethane class high molecular polymer, can be substantially improved the stability of dispersion, can make polymerization
Thing film has good resistance to water, adhesive force and adhesion strength.
For this purpose, the present invention is adopted the following technical scheme that：A kind of preparation of cross-linking block-graft type high molecular polymer
Method, which comprises the steps：With glyceryl monostearate and polyisocyanates as raw material, catalyst is added to be reacted, instead
After answering 1.5-3.5 hours, the polyols blend reaction with trimethylolpropane poly glycol monomethyl ether and other polyhydric alcohol compositions,
After continuing reaction 2.5-3.5 hours, chain extender is added, control temperature adds end-blocking at 40-50 DEG C after reaction 0.5-1 hours
Agent, is incubated about 10-60 minutes, is cooled to room temperature, obtains base polyurethane prepolymer for use as；Water stirring 10-20 minutes are added, revolving is obtained final product can
Crosslinked block-graft type polyurethane class high molecular polymer；
Other described polyhydric alcohol are the polyether polyol of block type, the one kind in polyether polyol, PEPA or
It is various.
The present invention with glyceryl monostearate, polyisocyanates as raw material, with trimethylolpropane poly glycol monomethyl ether
(TMPEG) and other polyhydric alcohol polyols blend reaction, finally carry out chain extension, end-blocking, emulsifying, distillation etc. generation one kind can hand over
Connection block-graft type polyurethane polymer.The polymer of present invention synthesis, its side chain have the water repellent chain alkyl of graft type
With the structure such as hydrophilic polyoxyethylene ether, therefore there is obvious parents' effect (similar to high-molecular surface active in polymer lateral chain
Agent)；Meanwhile, also the water repellent segmented polyurethane (group such as isocyanates) with block type and hydrophilic gather on main polymer chain
The structures such as oxygen vinyl Ether, therefore also there is on main polymer chain obvious parents' effect.
Exactly this unique block-graft type structure so that the polymer performance of the present invention is totally different from traditional meaning
Block type polyurethane copolymer simple in justice.On the one hand, this is aggregated in main chain and side chain all has amphiphilic structure, polymer
Steric configuration can need to be adjusted flexibly according to practical situation with conformation, so all having to dyestuff, pigment and other materials
There are extraordinary emulsifying, dispersion and stable, the stability of dispersion can be substantially improved；On the other hand, the polymer
Substantial amounts of active group is remained in structure, during heating can with hydroxyl, amino or itself be crosslinked, polymer can be made
Film has good resistance to water, adhesive force and adhesion strength.
Further, if chain extender is anionic or cationic, also need to add appropriate nertralizer after being cooled to room temperature
(if chain extender is nonionic, then need not add nertralizer), then obtains base polyurethane prepolymer for use as；Described nertralizer is three
One kind in ethamine, ammonia, sodium hydroxide, hydrochloric acid, acetic acid.
Further, above-mentioned raw materials consumption is as follows by mass percentage:Polyisocyanates：14.1-47.9%, single Hard Fat
Acid glyceride：10-20%, chain extender：0.3-1.0%, polyols blend：25-72%, end-capping reagent：2-10%, nertralizer：0-
4.8%；By mass percentage, trimethylolpropane poly glycol monomethyl ether accounts for the 14.5-75% of polyols blend.
Further, glyceryl monostearate and polyisocyanates add appropriate solvent when reacting with polyols blend,
Reduce system viscosity, it is ensured that reaction is smoothed out；Described solvent can be acetone, butanone, ethyl acetate, butyl acetate,
N- methyl pyrrole network alkanones etc..
Further, the polyether polyol of described block type is polypropylene glycol-polyethylene glycol Propylene Glycol；Described
Polyether polyol is Polyethylene Glycol, polypropylene glycol, one or more in polytetrahydrofuran diol；Described PEPA is
One kind in 10PE27, polypropylene glycol adipate, poly adipate succinic acid ester, polybutene naphthalate
Or it is various.
Further, described polyisocyanates be aromatic diisocyanate, the one kind in aliphatic diisocyanate
Or two kinds；
Described aromatic diisocyanate is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, penylene two are different
One or more in cyanate, biphenyl diisocyanate, XDI；Described two Carbimide. of aliphatic
Ester is isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, two Carbimide. of dimethylene
One or more in ester, methylcyclohexane diisocyanate.
Further, described catalyst is organotin or organic base, and described organotin is stannous octoate, tin dilaurate
One or more in dibutyl tin, described organic base be triethylamine, three ethyleneamineses, propane diamine, in DMA
One or more.
Further, described chain extender is the one kind or combination in any in following compounds：Double hydroxymethyl propionic acids, dihydroxy
Base half ester, second diaminourea ethyl sulfonic acid sodium, 1,4- butanediol 2- sodium sulfonates, 1,4- butanediol 2- sodium sulfonate derivatives, N- first
Base diethanolamine, N- ethyldiethanolamines, N- propyl group diethanolamine, N- benzyl diethanolamine, tertiarybutyldiethanolamine, dimethyl
Ethanolamine, diethanolamine, 1,4- butanediols.
Further, described end-capping reagent is acetone oxime, diacetylmonoxime, cyclohexanone-oxime, ξ-caprolactam, 3,5- dimethyl pyrazoles
One kind in azoles, butanol, 1,2,4- triazoles, nonyl phenol.
Further, the structural formula of trimethylolpropane poly glycol monomethyl ether (TMPEG, Mn=1000-2000) is as follows：
N=18-24.
The device have the advantages that as follows：Cross-linking block-distinctive structure of grafting type polyurethane significantly can be carried
High its emulsifying capacity so as to excellent surface property, strengthen the dispersion stabilization of system, to dyestuff, pigment and other things
Matter has extraordinary emulsifying, dispersion and stable effect；Polymer terminal group NCO is closed agent end-blocking simultaneously, with good
Crosslinking function and particle binding ability, make film have good resistance to water, adhesive force and adhesion strength.
Specific embodiment
The present invention is described in further detail with reference to embodiment.
Embodiment 1：Be 120 DEG C in temperature, vacuum be under conditions of 0.09MPa to molecular weight be 1000 TMPEG and
Molecular weight is that, after the mixture of 1200 Polyethylene Glycol carries out vacuum distillation 1 hour, cooling sealing is stand-by.To with agitator and
10.7g glyceryl monostearates are added in the four-hole boiling flask of thermometer, temperature is 120 DEG C, under conditions of vacuum is 0.09MPa
Vacuum distillation 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin laurates is added, then Deca 12g toluene di-isocyanate(TDI),
Stirring is warming up to 80-85 DEG C, reacts 2 hours.It is 1200 to be subsequently adding TMPEG that 33.53g molecular weight is 1000 and molecular weight
Polyethylene Glycol mixture (wherein 15.24g TMPEG；18.29g Polyethylene Glycol), and add 20g butanone to be diluted, continue anti-
Answer 3 hours.0.2g1 is subsequently adding, 4- butanediols after 45 DEG C are reacted 45 minutes, add the diacetylmonoxime of 1.06g, continue reaction half
Hour.Room temperature is cooled to, 230g deionized waters high-speed stirred is added 10 minutes, revolving removes solvent and obtains solid containing about 20%
Cross-linking block-grafting type polyurethane.
Embodiment 2：Temperature be 120 DEG C, vacuum be 0.09MPa under conditions of molecular weight is 1200 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of Polyethylene Glycol, cooling sealing is stand-by.To four mouthfuls with agitator and thermometer
9.87g glyceryl monostearates are added in flask, temperature is 120 DEG C, and vacuum is little for vacuum distillation 1 under conditions of 0.09MPa
When.60 DEG C are cooled to, 0.02g dibutyl tin laurates is added, then Deca 11.67g toluene di-isocyanate(TDI), stirring heats up
To 80-85 DEG C, react 2 hours.Be subsequently adding 29.94g molecular weight be 1200 TMPEG and Polyethylene Glycol mixture (wherein
23.02g TMPEG；6.92g Polyethylene Glycol), and add 20g ethyl acetate to be diluted, continue reaction 3 hours.It is subsequently adding
0.2g1,4- butanediol, after 45 DEG C are reacted 45 minutes, adds the 3，5-dimethylpyrazole of 2.37g, continues reaction half an hour.Cooling
To room temperature, add 220g deionized waters high-speed stirred 10 minutes, revolving remove solvent obtain it is solid containing about 20% it is cross-linking
Block-grafting type polyurethane.
Embodiment 3：Temperature be 120 DEG C, vacuum be 0.09MPa under conditions of molecular weight is 2000 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of 10PE27, cooling sealing is stand-by.To with agitator and temperature
In the four-hole boiling flask of meter add 14.34g glyceryl monostearates, temperature be 120 DEG C, vacuum be 0.09MPa under conditions of subtract
Pressure distillation 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin laurates are added, then Deca 29g toluene di-isocyanate(TDI), stirs
Mix and be warming up to 80-85 DEG C, react 2 hours.It is subsequently adding TMPEG and polyadipate ethylene glycol that 71.5g molecular weight is 2000
Mixture (the wherein 10.37g TMPEG of ester；61.13g 10PE27s), and add 20g butanone to be diluted, after
Continuous reaction 3 hours.The double hydroxymethyl propionic acids of 5.98g are subsequently adding, the diacetylmonoxime of 8.0g after 45 DEG C are reacted 45 minutes, are added, is continued
Reaction half an hour.Room temperature is cooled to, the triethylamine of 4.6g is added, continues stir about after 1 hour, add 540g deionized waters at a high speed
Stirring 10 minutes, revolving remove solvent and obtain solid containing about 20% cross-linking block-grafting type polyurethane.
Embodiment 4：Temperature be 120 DEG C, vacuum be 0.09MPa under conditions of molecular weight is 1000 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of Polyethylene Glycol, cooling sealing is stand-by.To four mouthfuls with agitator and thermometer
14.34g glyceryl monostearates are added in flask, temperature is 120 DEG C, and vacuum is little for vacuum distillation 1 under conditions of 0.09MPa
When.60 DEG C are cooled to, 0.02g triethylamines is added, then Deca 29g toluene di-isocyanate(TDI), stirring is warming up to 80-85 DEG C, instead
Answer 2 hours.It is subsequently adding 35.75g molecular weight and is 1000 TMPEG and mixture (wherein TMPEG and the poly- second of Polyethylene Glycol
Glycol is 17.875g), and add 20gN- methyl pyrrole network alkanones to be diluted, continue reaction 3 hours.It is subsequently adding 5.35g
N methyldiethanol amine, after 45 DEG C are reacted 45 minutes, adds the butanol of 6.8g, continues reaction half an hour.Room temperature is cooled to, is added
The acetic acid of 2.7g, continues stir about after 1 hour, adds 380g deionized waters high-speed stirred 10 minutes, and revolving removes solvent and obtains final product
To solid containing about 20% cross-linking block-grafting type polyurethane.
Embodiment 5：Temperature be 120 DEG C, vacuum be 0.09MPa under conditions of molecular weight is 1200 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of polypropylene glycol-polyethylene glycol Propylene Glycol, cooling sealing is stand-by.Stir to carrying
10.7g glyceryl monostearates are added in mixing the four-hole boiling flask of device and thermometer, temperature is 120 DEG C, and vacuum is 0.09MPa's
Under the conditions of vacuum distillation 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin laurates is added, then the different Fo Er of Deca 15.32g
Ketone diisocyanate, stirring are warming up to 80-85 DEG C, react 2 hours.It is subsequently adding the TMPEG that 36.58g molecular weight is 1200
(wherein TMPEG and polypropylene glycol-polyethylene glycol Propylene Glycol are equal with the mixture of polypropylene glycol-polyethylene glycol Propylene Glycol
For 18.29g), and add 20g butanone to be diluted, continue reaction 3 hours.It is subsequently adding 0.2g1,4- butanediols, 45 DEG C of reactions
The diacetylmonoxime of 1.06g after 45 minutes, is added, continues reaction half an hour.Room temperature is cooled to, 260g deionized water high-speed stirred is added
10 minutes, revolving removed solvent and obtains solid containing about 20% cross-linking block-grafting type polyurethane.
The above, is only presently preferred embodiments of the present invention, not makees any form to technical scheme
On restriction.It is every according to the present invention technical spirit above example is made any simple modification, equivalent variations with repair
Decorations, each fall within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cross-linking block-graft type high molecular polymer, which comprises the steps：It is sweet with monostearate
Grease and polyisocyanates are raw material, add catalyst to be reacted, after reaction 1.5-3.5 hours, poly- with trimethylolpropane
The polyols blend reaction of glycol monoethyl ether and other polyhydric alcohol compositions, after continuing reaction 2.5-3.5 hours, adds chain extension
Agent, control temperature after reaction 0.5-1 hours, add end-capping reagent, are incubated about 10-60 minutes, are cooled to room temperature, obtain at 40-50 DEG C
To base polyurethane prepolymer for use as；Water stirring 10-20 minutes, revolving is added to obtain final product cross-linking block-graft type polyurethane class high molecular and gather
Compound；
Other described polyhydric alcohol are the polyether polyol of block type, one or more in polyether polyol, PEPA.
2. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1, it is characterised in that
If chain extender is anionic or cationic, also need to add appropriate nertralizer after being cooled to room temperature, then obtain polyurethane pre-
Aggressiveness；Described nertralizer is triethylamine, ammonia, sodium hydroxide, hydrochloric acid, the one kind in acetic acid.
3. the preparation method of cross-linking block-graft type high molecular polymer according to claim 2, it is characterised in that
Above-mentioned raw materials consumption is as follows by mass percentage:Polyisocyanates：14.1-47.9%, glyceryl monostearate：10-20%,
Chain extender：0.3-1.0%, polyols blend：25-72%, end-capping reagent：2-10%, nertralizer：0-4.8%；By mass percentage
Meter, trimethylolpropane poly glycol monomethyl ether account for the 14.5-75% of polyols blend.
4. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1, it is characterised in that
Glyceryl monostearate and polyisocyanates add appropriate solvent when reacting with polyols blend, reduce system viscosity, it is ensured that
That what is reacted is smoothed out；Described solvent is acetone, butanone, ethyl acetate, butyl acetate or N- methyl pyrrole network alkanones.
5. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
It is,
The polyether polyol of described block type is polypropylene glycol-polyethylene glycol Propylene Glycol；Described polyether polyol is poly-
One or more in ethylene glycol, polypropylene glycol, polytetrahydrofuran diol；Described PEPA is polyadipate ethylene glycol
One or more in ester, polypropylene glycol adipate, poly adipate succinic acid ester, polybutene naphthalate.
6. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
Be that described polyisocyanates is aromatic diisocyanate, one or two in aliphatic diisocyanate；
Described aromatic diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two Carbimide. of penylene
One or more in ester, biphenyl diisocyanate, XDI；Described aliphatic diisocyanate is
Isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dimethylene diisocyanate,
One or more in methylcyclohexane diisocyanate.
7. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
It is that described catalyst is organotin or organic base, described organotin is stannous octoate, in dibutyl tin laurate
One or more, described organic base is triethylamine, three ethyleneamineses, propane diamine, the one kind or many in DMA
Kind.
8. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
It is,
Described chain extender is one kind or combination in any in following compounds：Double hydroxymethyl propionic acids, dihydroxy half ester, second diamino
Base ethyl sulfonic acid sodium, 1,4- butanediol 2- sodium sulfonates, 1,4- butanediol 2- sodium sulfonate derivatives, N methyldiethanol amine, N-
Ethyldiethanolamine, N- propyl group diethanolamine, N- benzyl diethanolamine, tertiarybutyldiethanolamine, dimethylethanolamine, diethanol
Amine, 1,4- butanediols.
9. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
It is,
Described end-capping reagent be acetone oxime, diacetylmonoxime, cyclohexanone-oxime, ξ-caprolactam, 3，5-dimethylpyrazole, butanol, 1,2,
One kind in 4- triazoles, nonyl phenol.
10. the preparation method of the cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, its feature
It is,
The structural formula of trimethylolpropane poly glycol monomethyl ether is as follows：
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610920547.2A CN106543402B (en) | 2016-10-21 | 2016-10-21 | A kind of preparation method of cross-linking block-graft type high molecular polymer |
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| CN201610920547.2A CN106543402B (en) | 2016-10-21 | 2016-10-21 | A kind of preparation method of cross-linking block-graft type high molecular polymer |
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| CN108129636A (en) * | 2017-12-19 | 2018-06-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic pectinate texture polysiloxane-polyurethane graft copolymer |
| CN109403045A (en) * | 2018-10-29 | 2019-03-01 | 江南大学 | A kind of preparation method and application of polyurethane-acrylate class water repellent |
| CN110527109A (en) * | 2019-09-03 | 2019-12-03 | 北京大学口腔医学院 | A kind of polyhydroxy dissaving polymer and preparation method and its application in dentistry composite resin |
| CN110591046A (en) * | 2019-09-10 | 2019-12-20 | 黄山中泽新材料有限公司 | Cross-linked ester-soluble polyurethane ink binder, and preparation method and application thereof |
| CN110746586A (en) * | 2019-11-08 | 2020-02-04 | 华中科技大学 | Preparation method of polyacrylate-polyester I-polyester II triblock copolymer |
| CN111995724A (en) * | 2020-08-31 | 2020-11-27 | 山东一诺威聚氨酯股份有限公司 | Low-polarity thermoplastic polyurethane elastomer and preparation method thereof |
| CN115073699A (en) * | 2022-06-14 | 2022-09-20 | 杭州柏医健康科技有限公司 | Temperature-insensitive polyurethane polymer and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108129636A (en) * | 2017-12-19 | 2018-06-08 | 传化智联股份有限公司 | A kind of preparation method of amphipathic pectinate texture polysiloxane-polyurethane graft copolymer |
| CN109403045A (en) * | 2018-10-29 | 2019-03-01 | 江南大学 | A kind of preparation method and application of polyurethane-acrylate class water repellent |
| CN109403045B (en) * | 2018-10-29 | 2020-10-09 | 高青如意纺织有限公司 | Preparation method and application of polyurethane-acrylate water repellent |
| CN110527109A (en) * | 2019-09-03 | 2019-12-03 | 北京大学口腔医学院 | A kind of polyhydroxy dissaving polymer and preparation method and its application in dentistry composite resin |
| CN110527109B (en) * | 2019-09-03 | 2021-06-11 | 北京大学口腔医学院 | Polyhydroxy hyperbranched polymer, preparation method and application thereof in dental composite resin |
| CN110591046A (en) * | 2019-09-10 | 2019-12-20 | 黄山中泽新材料有限公司 | Cross-linked ester-soluble polyurethane ink binder, and preparation method and application thereof |
| CN110746586A (en) * | 2019-11-08 | 2020-02-04 | 华中科技大学 | Preparation method of polyacrylate-polyester I-polyester II triblock copolymer |
| CN111995724A (en) * | 2020-08-31 | 2020-11-27 | 山东一诺威聚氨酯股份有限公司 | Low-polarity thermoplastic polyurethane elastomer and preparation method thereof |
| CN115073699A (en) * | 2022-06-14 | 2022-09-20 | 杭州柏医健康科技有限公司 | Temperature-insensitive polyurethane polymer and application thereof |
| CN115073699B (en) * | 2022-06-14 | 2024-01-26 | 杭州柏医健康科技有限公司 | Temperature-insensitive polyurethane polymer and application thereof |
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