CN106543402B - 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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- CN106543402B CN106543402B CN201610920547.2A CN201610920547A CN106543402B CN 106543402 B CN106543402 B CN 106543402B CN 201610920547 A CN201610920547 A CN 201610920547A CN 106543402 B CN106543402 B CN 106543402B
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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
- C08G18/65—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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/286—Oximes
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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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
- C08G18/4833—Polyethers containing oxyethylene units
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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
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Abstract
The invention discloses a kind of preparation methods of cross-linking block-graft type high molecular polymer.Current some polyurethanes amphiphilic polymers constrain it in the extensive use in the fields such as emulsion polymerization, pigment dispersion due to the limitation of its hydrophilic segment and oleophylic segment Space expanding.The present invention is using glycerin monostearate and polyisocyanates as raw material, it is reacted with the polyols blend of trimethylolpropane poly glycol monomethyl ether and other polyalcohols, finally carries out chain extension, sealing end, emulsification, distillation etc. and generate a kind of cross-linking block-graft type polyurethane class high molecular polymer.The distinctive block of the polymer-graft type structure makes it have preferable surface-active, cooperates with the active group in its structure, make its fields such as pigment dispersing agent, stabilizer and emulsion polymerization with good application prospect;Remain a large amount of active group on polymer simultaneously, when heating can with hydroxyl, amino or itself be crosslinked, can make polymer film that there is good water resistance, adhesive force and adhesion strength.
Description
Technical field
It is specifically a kind of poly- in pigment dispersing agent, stabilizer and lotion the present invention relates to chemical field
There is cross-linking block-graft type polyurethane class high molecular polymer preparation method of preferable application prospect in the fields such as conjunction.
Background technique
Aqueous polyurethane (WPU) is that have compared with solvent borne polyurethane by the binary colloidal system of decentralized medium of water
It non-ignitable, the advantages that smell is small, free from environmental pollution, energy saving, operation is easy to process, thus increasingly attracts much attention,
And it is gradually applied in fields such as dispersing agent, emulsion polymerizations.Contain a large amount of isocyanates in one side aqueous polyurethane
Base, hydroxyl isoreactivity group can pass through chemical bond or molecule with hydroxyl, the amino etc. on fabric or dyestuff at a lower temperature
Between active force be combined, can be improved the dispersion stabilization of system, enhance the fastness such as washable of polymer;On the other hand in cream
Water resistance, adhesive force and the adhesion strength that can be improved film in liquid polymerization using water-based polyurethane macromolecule emulsifier, are increased
Its strong film forming and elasticity.
Chinese patent 201510889084.3 discloses a kind of Y type three block non-ion aqueous polyurethane class surface-active
Agent, it is prepared by glycerin monostearate, isocyanates and polyoxyethylene monomethyl ether.The patent claims in its molecular structure
The surface tension of solution can be effectively reduced in methyl structural, and is mainly used in the displacement of reservoir oil, sewage treatment etc., have green, life
The advantages that object compatibility is good, however since its hydrophilic segment is shorter, 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, it is by the two of hydrophobic
First alcohol or the heating reaction of diamine or naphthols and isocyanates add polyethylene glycol or polyethyleneglycol first after solvent dilution
Ether reacts to obtain with the mixture of catalyst.The patent, which claims the dispersing agent to have, makes granules of pigments is uniformly dispersed and stability is good etc.
Advantage, but since its overall structure is straight chain, the hydrated sheath external interference resistance that hydrophilic segment is formed is weaker.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the problems of the above-mentioned prior art, provide 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 to polymerize
Object film has good water resistance, adhesive force and adhesion strength.
For this purpose, the present invention adopts the following technical scheme that: a kind of preparation of cross-linking block-graft type high molecular polymer
Method comprising following steps: using glycerin monostearate and polyisocyanates as raw material, catalyst is added and is reacted, instead
After answering 1.5-3.5 hours, the polyols blend formed with trimethylolpropane poly glycol monomethyl ether and other polyalcohols reacts,
After the reaction was continued 2.5-3.5 hours, chain extender is added, controls temperature at 40-50 DEG C, after reaction 0.5-1 hours, sealing end is added
Agent keeps the temperature about 10-60 minutes, is cooled to room temperature, obtains base polyurethane prepolymer for use as;Water is added to stir 10-20 minutes, rotates and to obtain the final product may be used
Crosslinked block-graft type polyurethane class high molecular polymer;
Other described polyalcohols be one of polyether polyol of block type, polyether polyol, polyester polyol or
It is a variety of.
The present invention is using glycerin monostearate, polyisocyanates as raw material, with trimethylolpropane poly glycol monomethyl ether
(TMPEG) it is reacted with the polyols blend of other polyalcohols, finally progress chain extension, sealing end, emulsification, distillation etc., which generate one kind, to hand over
Join block-graft type polyurethane polymer.The polymer that the present invention synthesizes, side chain have the water repellent chain alkyl of graft type
With the structures such as hydrophilic polyoxyethylene ether, therefore there is apparent parents' effect (to be similar to high-molecular surface active in polymer lateral chain
Agent);Meanwhile also the water repellent segmented polyurethane (groups such as isocyanates) with block type and hydrophilic gathering on main polymer chain
The structures such as ethylene oxide ether, therefore also there is apparent parents' effect on main polymer chain.
Exactly this unique block-graft type structure, so that polymer performance of the invention is totally different from traditional meaning
Simple block type polyurethane copolymer in justice.On the one hand, this, which is aggregated in main chain and side chain all, has amphiphilic structure, polymer
Steric configuration can be adjusted flexibly according to the actual situation with conformation, so all having to dyestuff, pigment and other substances
Play the role of it is extraordinary emulsification, dispersion and it is stable, the stability of dispersion can be substantially improved;On the other hand, the polymer
Remain a large amount of active group in structure, when heating can with hydroxyl, amino or itself be crosslinked, polymer can be made
Film has good water resistance, adhesive force and adhesion strength.
Further, it if chain extender is anionic or cationic, also needs that appropriate neutralizer is added after being cooled to room temperature
(such as chain extender be it is non-ionic, then do not need be added neutralizer), then obtain base polyurethane prepolymer for use as;The neutralizer is three
One of ethamine, ammonium hydroxide, sodium hydroxide, hydrochloric acid, acetic acid.
Further, above-mentioned raw materials dosage is as follows by mass percentage: polyisocyanates: 14.1-47.9%, single stearic
Acid glyceride: 10-20%, chain extender: 0.3-1.0%, polyols blend: 25-72%, end-capping reagent: 2-10%, neutralizer: 0-
4.8%;By mass percentage, trimethylolpropane poly glycol monomethyl ether accounts for the 14.5-75% of polyols blend.
Further, suitable solvent is added when glycerin monostearate and polyisocyanates are reacted with polyols blend,
System viscosity is reduced, guarantees going on smoothly for reaction;The solvent can be acetone, butanone, ethyl acetate, butyl acetate,
N- methyl pyrrole network alkanone etc..
Further, the polyether polyol of the block type is polypropylene glycol-polyethylene glycol propylene glycol;Described
Polyether polyol is one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or a variety of;The polyester polyol is
One of polyethylene glycol adipate, polypropylene glycol adipate, poly adipate succinic acid ester, polybutene naphthalate
Or it is a variety of.
Further, the polyisocyanates is one of aromatic diisocyanate, aliphatic diisocyanate
Or two kinds;
The aromatic diisocyanate is that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, penylene two are different
One of cyanate, biphenyl diisocyanate, benzene dimethylene diisocyanate are a variety of;The aliphatic diisocyanate
Ester is isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dimethylene diisocyanate
One of ester, methylcyclohexane diisocyanate are a variety of.
Further, the catalyst is organotin or organic base, and the organotin is stannous octoate, tin dilaurate
One of dibutyl tin is a variety of, and the organic base is triethylamine, in three ethyleneamines, propane diamine, n,N-Dimethylaniline
It is one or more.
Further, the chain extender is one of following compounds or any combination: double hydroxymethyl propionic acids, dihydroxy
Base half ester, second diamino ethanesulfonic acid sodium, 1,4- butanediol 2- sodium sulfonate, 1,4- butanediol 2- sodium sulfonate derivative, N- first
Base diethanol amine, N- ethyldiethanolamine, N- propyl diethanol amine, N- benzyl diethanol amine, tertiarybutyldiethanolamine, dimethyl
Ethanol amine, diethanol amine, 1,4- butanediol.
Further, the end-capping reagent is acetoxime, diacetylmonoxime, cyclohexanone oxime, ξ-caprolactam, 3,5- dimethyl pyrazole
Azoles, butanol, 1, one of 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 can be mentioned substantially
Its high emulsifying capacity, makes it have excellent surface property, enhances the dispersion stabilization of system, to dyestuff, pigment and other objects
Matter have the function of it is extraordinary emulsification, dispersion and it is stable;Polymer terminal group NCO is closed agent sealing end simultaneously, has good
It is crosslinked function and particle binding performance, makes film that there is good water resistance, adhesive force and adhesion strength.
Specific embodiment
The present invention is described in further detail below with reference to embodiment.
Embodiment 1: temperature be 120 DEG C, vacuum degree be 0.09MPa under conditions of to molecular weight be 1000 TMPEG and
After the mixture for the polyethylene glycol that molecular weight is 1200 carries out vacuum distillation 1 hour, cooling sealing is stand-by.To with blender and
10.7g glycerin monostearate is added in the four-hole boiling flask of thermometer, temperature is 120 DEG C, under conditions of vacuum degree is 0.09MPa
Vacuum distillation 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin dilaurate is added, 12g toluene di-isocyanate(TDI) is then added dropwise,
Stirring is warming up to 80-85 DEG C, reacts 2 hours.Then the TMPEG and molecular weight that addition 33.53g molecular weight is 1000 are 1200
Polyethylene glycol mixture (wherein 15.24g TMPEG;18.29g polyethylene glycol), and 20g butanone is added and is diluted, continue anti-
It answers 3 hours.Then 0.2g1 is added, the diacetylmonoxime of 1.06g is added after 45 DEG C are reacted 45 minutes in 4- butanediol, and the reaction was continued partly
Hour.It is cooled to room temperature, is added 230g deionized water high-speed stirred 10 minutes, revolving removal solvent obtains solid containing about 20%
Cross-linking block-grafting type polyurethane.
Embodiment 2: temperature be 120 DEG C, vacuum degree be 0.09MPa under conditions of be to molecular weight 1200 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of polyethylene glycol, cooling sealing is stand-by.To four mouthfuls with blender and thermometer
9.87g glycerin monostearate is added in flask, temperature is 120 DEG C, and vacuum distillation 1 is small under conditions of vacuum degree is 0.09MPa
When.60 DEG C are cooled to, 0.02g dibutyl tin dilaurate is added, 11.67g toluene di-isocyanate(TDI), stirring heating is then added dropwise
To 80-85 DEG C, react 2 hours.Then the TMPEG and polyethylene glycol mixture that addition 29.94g molecular weight is 1200 are (wherein
23.02g TMPEG;6.92g polyethylene glycol), and 20g ethyl acetate is added and is diluted, the reaction was continued 3 hours.Then it is added
After 45 DEG C are reacted 45 minutes 3, the 5- dimethyl pyrazole of 2.37g is added, the reaction was continued half an hour in 0.2g1,4- butanediol.It is cooling
To room temperature, be added 220g deionized water high-speed stirred 10 minutes, revolving removal solvent be obtain it is solid containing about 20% it is cross-linking
Block-grafting type polyurethane.
Embodiment 3: temperature be 120 DEG C, vacuum degree be 0.09MPa under conditions of be to molecular weight 2000 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of polyethylene glycol adipate, cooling sealing is stand-by.To with blender and temperature
14.34g glycerin monostearate is added in the four-hole boiling flask of meter, temperature is 120 DEG C, and vacuum degree subtracts under conditions of being 0.09MPa
Pressure distillation 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin dilaurate is added, 29g toluene di-isocyanate(TDI) is then added dropwise, stirs
It mixes and is warming up to 80-85 DEG C, react 2 hours.Then TMPEG and the polyadipate ethylene glycol that 71.5g molecular weight is 2000 is added
Mixture (the wherein 10.37g TMPEG of ester;61.13g polyethylene glycol adipate), and 20g butanone is added and is diluted, after
Continuous reaction 3 hours.Then the bis- hydroxymethyl propionic acids of 5.98g are added, the diacetylmonoxime of 8.0g is added after 45 DEG C are reacted 45 minutes, continue
React half an hour.It is cooled to room temperature, the triethylamine of 4.6g is added, continue stir about after 1 hour, 540g deionized water high speed is added
Stirring 10 minutes, revolving removal solvent are to obtain cross-linking block-grafting type polyurethane containing about 20% admittedly.
Embodiment 4: temperature be 120 DEG C, vacuum degree be 0.09MPa under conditions of be to molecular weight 1000 TMPEG
After carrying out vacuum distillation 1 hour with the mixture of polyethylene glycol, cooling sealing is stand-by.To four mouthfuls with blender and thermometer
14.34g glycerin monostearate is added in flask, temperature is 120 DEG C, and vacuum distillation 1 is small under conditions of vacuum degree is 0.09MPa
When.60 DEG C are cooled to, 0.02g triethylamine is added, 29g toluene di-isocyanate(TDI) is then added dropwise, stirring is warming up to 80-85 DEG C, instead
It answers 2 hours.Then it is 1000 TMPEG and mixture (wherein TMPEG and the poly- second of polyethylene glycol that 35.75g molecular weight, which is added,
Glycol is 17.875g), and 20gN- methyl pyrrole network alkanone is added and is diluted, the reaction was continued 3 hours.Then 5.35g is added
After 45 DEG C are reacted 45 minutes the butanol of 6.8g is added, the reaction was continued half an hour in N methyldiethanol amine.It is cooled to room temperature, is added
The acetic acid of 2.7g continues stir about after 1 hour, is added 380g deionized water high-speed stirred 10 minutes, and revolving removal solvent to obtain the final product
To solid containing the cross-linking block-grafting type polyurethane for being about 20%.
Embodiment 5: temperature be 120 DEG C, vacuum degree be 0.09MPa under conditions of be to molecular weight 1200 TMPEG
After carrying out vacuum distillation 1 hour with polypropylene glycol-polyethylene glycol propylene glycol mixture, cooling sealing is stand-by.It is stirred to having
Addition 10.7g glycerin monostearate in the four-hole boiling flask of device and thermometer is mixed, temperature is 120 DEG C, and vacuum degree is 0.09MPa's
Under the conditions of be evaporated under reduced pressure 1 hour.60 DEG C are cooled to, 0.02g dibutyl tin dilaurate is added, the different Fo Er of 15.32g is then added dropwise
Ketone diisocyanate, stirring are warming up to 80-85 DEG C, react 2 hours.Then the TMPEG that 36.58g molecular weight is 1200 is added
(wherein TMPEG and polypropylene glycol-polyethylene glycol propylene glycol are equal with polypropylene glycol-polyethylene glycol propylene glycol mixture
For 18.29g), and 20g butanone is added and is diluted, the reaction was continued 3 hours.Then 0.2g1,4- butanediol, 45 DEG C of reactions are added
After 45 minutes, the diacetylmonoxime of 1.06g is added, the reaction was continued half an hour.It is cooled to room temperature, 260g deionized water high-speed stirred is added
10 minutes, revolving removal solvent was to obtain cross-linking block-grafting type polyurethane containing about 20% admittedly.
The above described is only a preferred embodiment of the present invention, not making any form to technical solution of the present invention
On limitation.According to the technical essence of the invention any simple modification to the above embodiments, equivalent variations and repair
Decorations, fall within the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of cross-linking block-graft type high molecular polymer comprising following steps: sweet with monostearate
Grease and polyisocyanates are raw material, and catalyst is added and is reacted, poly- with trimethylolpropane after reaction 1.5-3.5 hours
The polyols blend reaction of glycol monoethyl ether and other polyalcohols composition, after the reaction was continued 2.5-3.5 hours, is added chain extension
Agent controls temperature at 40-50 DEG C, after reaction 0.5-1 hours, end-capping reagent is added, keeps the temperature 10-60 minutes, is cooled to room temperature, obtains
Base polyurethane prepolymer for use as;Water is added to stir 10-20 minutes, rotates up to cross-linking block-graft type polyurethane class high molecular polymerization
Object;
Other described polyalcohols are one of polyether polyol, polyether polyol, polyester polyol of block type or a variety of;
The polyether polyol of the block type is polypropylene glycol-polyethylene glycol propylene glycol;The polyether polyol is poly-
One of ethylene glycol, polypropylene glycol, polytetrahydrofuran diol are a variety of;The polyester polyol is polyadipate ethylene glycol
One of ester, polypropylene glycol adipate, poly adipate succinic acid ester, polybutene naphthalate are a variety of.
2. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1, which is characterized in that
When the chain extender is anionic or cationic, also needs that appropriate neutralizer is added after being cooled to room temperature, then obtain poly- ammonia
Ester performed polymer;The neutralizer is one of triethylamine, ammonium hydroxide, sodium hydroxide, hydrochloric acid, acetic acid.
3. the preparation method of cross-linking block-graft type high molecular polymer according to claim 2, which is characterized in that
Above-mentioned raw materials dosage is as follows by mass percentage: polyisocyanates: 14.1-47.9%, glycerin monostearate: 10-20%,
Chain extender: 0.3-1.0%, polyols blend: 25-72%, end-capping reagent: 2-10%, neutralizer: 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, which is characterized in that
Suitable solvent is added in glycerin monostearate and polyisocyanates when reacting with polyols blend, reduce system viscosity, guarantees
Reaction is gone on smoothly;The solvent is acetone, butanone, ethyl acetate, butyl acetate or N-Methyl pyrrolidone.
5. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, feature
It is, the polyisocyanates is one or both of aromatic diisocyanate, aliphatic diisocyanate;
The aromatic diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, penylene diisocyanate
One of ester, biphenyl diisocyanate, benzene dimethylene diisocyanate are a variety of;The aliphatic diisocyanate is
Isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dimethylene diisocyanate,
One of methylcyclohexane diisocyanate is a variety of.
6. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, feature
It is, the catalyst is organotin or organic base, and the organotin is stannous octoate, in dibutyl tin dilaurate
One or more, the organic base is one of triethylamine, three ethyleneamines, propane diamine, n,N-Dimethylaniline or more
Kind.
7. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, feature
It is,
The chain extender is one of following compounds or any combination: double hydroxymethyl propionic acids, dihydroxy half ester, second diamino
Base ethanesulfonic acid sodium, 1,4- butanediol 2- sodium sulfonate, 1,4- butanediol 2- sodium sulfonate derivative, N methyldiethanol amine, N-
Ethyldiethanolamine, N- propyl diethanol amine, N- benzyl diethanol amine, tertiarybutyldiethanolamine, dimethylethanolamine, diethanol
Amine, 1,4- butanediol.
8. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, feature
It is,
The end-capping reagent be acetoxime, diacetylmonoxime, cyclohexanone oxime, ξ-caprolactam, 3,5- dimethyl pyrazole, butanol, 1,2,
One of 4- triazole, nonyl phenol.
9. the preparation method of cross-linking block-graft type high molecular polymer according to claim 1,2 or 3, feature
It is,
The structural formula of trimethylolpropane poly glycol monomethyl ether is as follows:
N=18-24.
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