CN105860085A - Method for preparing modified polyurethane - Google Patents
Method for preparing modified polyurethane Download PDFInfo
- Publication number
- CN105860085A CN105860085A CN201610476138.8A CN201610476138A CN105860085A CN 105860085 A CN105860085 A CN 105860085A CN 201610476138 A CN201610476138 A CN 201610476138A CN 105860085 A CN105860085 A CN 105860085A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyurethane
- weight
- epoxy resin
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 31
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 150000005846 sugar alcohols Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- -1 acrylic ester Chemical class 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- DBXBTMSZEOQQDU-UHFFFAOYSA-N 3-hydroxyisobutyric acid Chemical compound OCC(C)C(O)=O DBXBTMSZEOQQDU-UHFFFAOYSA-N 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 claims 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 150000002440 hydroxy compounds Chemical class 0.000 claims 1
- 229920005862 polyol Polymers 0.000 abstract description 2
- 150000003077 polyols Chemical class 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- VXTMLLAYZATZIB-UHFFFAOYSA-N 3,3-dihydroxy-2-methylbutanoic acid Chemical compound OC(=O)C(C)C(C)(O)O VXTMLLAYZATZIB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08G18/08—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
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
- C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
-
- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a method for preparing modified polyurethane. The method includes operation steps of firstly, arranging polyol, diisocyanate, dihydroxyl carboxylic acid and chain extenders in reaction kettles in the existence of nitrogen; secondly, cooling polyurethane prepolymers obtained at the first step until the temperatures of the polyurethane prepolymers are lower than 45 DEG C, and adding organic amine, silane coupling agents, deionized water and diamine into the polyurethane prepolymers; thirdly, sequentially adding water phases and oil phases into organic modified polyurethane obtained at the second step; fourthly, adding epoxy resin into organic silicone/acrylate-modified polyurethane obtained at the third step. The method has the advantages that polyurethane is sequentially modified by organic silicone, acrylate and the epoxy resin, the flexibility and the water resistance of the polyurethane can be improved by the organic silicon-modified polyurethane, mechanical properties of the polyurethane can be enhanced by the acrylate-modified polyurethane, the stability and the cohesiveness of the polyurethane can be improved by epoxy resin-modified polyurethane, and accordingly the water-resistant modified polyurethane which is high in strength and stability can be obtained by the aid of the method.
Description
Technical field
The present invention relates to technical field of macromolecules, particularly relate to the preparation method of a kind of modified polyurethane.
Background technology
Along with the enhancing of people's environmental consciousness, material safety problem is paid attention to.Polyurethane have do not fire,
The advantages such as smell is little, nontoxic, pollution-free, energy-conservation, easy to operate, be the most extensively used as leather finishing agent,
Textile auxiliary, paper industry auxiliary agent, coating and adhesive etc., its product is successfully applied to light textile, skin
The industries such as leather, timber processing, building, papermaking.Especially in field of compound material, polyurethane can be passed through
Spray on fabric after such as luminescent material, ultraviolet ray-resistant material etc. mix with functional material, thus obtain
Obtain function fabric.
But, aqueous polyurethane is adopted and is used water as solvent, the stability in storage or transportation
Poor, lamination easily occurs, caking property is poor.And, after aqueous polyurethane is combined with base material,
Owing to the surface tension of WATER AS FLOW MEDIUM is too big, the poor easy suction of polyurethane resistance to water after substrate surface film forming
Water, film forming fastness is relatively low to be easily separated with base material, and the product feel after spraying is harder.
In view of this, it is necessary to polyurethane of the prior art is improved, to solve above-mentioned asking
Topic.
Summary of the invention
It is an object of the invention to disclose a kind of preparation method having modified polyurethane, a kind of in order to provide
Preparation has the method for the modified polyurethane of resistance to water, high-tenacity and high stability.
For achieving the above object, the invention provides the preparation method of a kind of modified polyurethane, including such as
Lower operating procedure:
Step one: be 50 parts of polyalcohols, 9 parts of diisocyanate, 60 parts of dihydroxy carboxylics by parts by weight
Acid and 35 parts of chain extenders are put in reactor under a nitrogen atmosphere, and reaction temperature is 70 DEG C～90 DEG C, reaction
Time is 2～4h；Continue to put into the double hydroxymethyl propionic acid of 3 parts of 2,2-in a kettle., 35 parts of acetone expand
Chain end capping reaction, reaction temperature is 50 DEG C～80 DEG C, and the reaction time is 2.5～4.5h, prepares polyurethane pre-
Aggressiveness；
Step 2: be that 50 parts of base polyurethane prepolymer for use as cool to 45 DEG C by the parts by weight obtained in step one
Hereinafter, add under stirring in 60 parts of organic amines with become salt, sequentially add 3.8 parts silane coupled
Agent, 40 parts of deionized waters and 35 parts of diamines, stirring reaction 25～45min, prepare organic-silicon-modified poly-
Urethane；
Step 3: be that 18 parts of lauryl sodium sulfate are dissolved in as aqueous phase in deionized water using parts by weight,
7.5 parts of azodiisobutyronitriles are dissolved in as oil phase in 25 parts of acrylic ester monomers, by aqueous phase and oil phase
In the 40 parts of organic silicon modified polyurethanes being added sequentially in step 2, stirring, then in condition of nitrogen gas
Under be warming up to 70 DEG C～90 DEG C, react 5～6h, obtain organosilicon/acrylate modified polyurethane；
Step 4: 55 parts of organosilicon/acrylate modifications that 25 parts of epoxy resin add in step 3 are gathered
In urethane, stirring, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h.
In some embodiments, the epoxy resin in described step 4 is selected from E-51, E-44, E-42
Bisphenol A epoxide resin.
In some embodiments, the molecular weight of the polyalcohol in described step one is between 1000 to 3000
Between.
In some embodiments, the dihydroxy carboxylic acids in described step one is dihydromethyl propionic acid or dihydroxy
Methylbutanoic acid.
In some embodiments, the chain extender in described step one is the low molecule that molecular weight is less than 400
Amount polyol.
Compared with prior art, the invention has the beneficial effects as follows: by organosilicon, acrylate and ring
Epoxy resins modified polyurethane successively, organic silicon modified polyurethane adds the flexibility of polyurethane and water-fast
Property, polymerization of acrylic modified polyurethane enhances the mechanical property of polyurethane, epoxy resin modification polyurethane
Improve stability and the caking property of polyurethane, thus obtain one and there is resistance to water, high-tenacity and height
The modified polyurethane of stability, the coated product modified polyurethane-coated obtained on sample has
There are the features such as soft, resistance to water is strong, adhesive fastness is high, ultimate strength is big.
Detailed description of the invention
The present invention is described in detail for each embodiment shown below, but it should explanation, these
Embodiment not limitation of the present invention, those of ordinary skill in the art are made according to these embodiments
Function, method or structure on equivalent transformation or replacement, belong to protection scope of the present invention it
In.
Embodiment one:
The preparation method of a kind of organosilicon/acrylate/epoxy resin modification polyurethane, including operating as follows
Step:
Step one: polyalcohol, diisocyanate, dihydroxy carboxylic acids and chain extender are put under a nitrogen atmosphere
Entering in reactor, reaction temperature is 70 DEG C～90 DEG C, and the reaction time is 2～4h；Continue to put in a kettle.
Entering 2, the double hydroxymethyl propionic acid of 2-, acetone carry out chain extension end capping reaction, and reaction temperature is 50 DEG C～80 DEG C, instead
It is 2.5～4.5h between Ying Shi, prepares base polyurethane prepolymer for use as；
Step 2: the base polyurethane prepolymer for use as obtained in step one is cooled to less than 45 DEG C, at stirring
In lower addition organic amine with become salt, sequentially add silane coupler, deionized water and diamine, stirring
Reaction 25～45min, prepares organic silicon modified polyurethane；
Step 3: lauryl sodium sulfate is dissolved in deionized water as aqueous phase, by azodiisobutyronitrile
Being dissolved in acrylic ester monomer as oil phase, aqueous phase and oil phase are added sequentially in step 2 is organic
In silicon modified polyurethane, stirring, it is warming up to 70 DEG C～90 DEG C the most under a nitrogen atmosphere, reacts 5～6h,
Obtain organosilicon/acrylate modified polyurethane；
Step 4: epoxy resin is added in the organosilicon/acrylate modified polyurethane in step 3, stir
Mixing, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h.
Wherein, the parts by weight of the polyalcohol in step one are 30 parts, the parts by weight of diisocyanate
Be 5 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 40 parts and chain extender be 20 parts, 2,2-
The parts by weight of double hydroxymethyl propionic acids are 2 parts, the parts by weight of acetone are 20 parts.
The parts by weight of the base polyurethane prepolymer for use as in step 2 are 30 parts, the parts by weight of organic amine are 40
Part, the parts by weight of silane coupler be 3 parts, the parts by weight of deionized water be 20 parts and diamine
Parts by weight be 25 parts；
The parts by weight of the lauryl sodium sulfate in step 3 are 10 parts, the parts by weight of deionized water
Be 30, the parts by weight of azodiisobutyronitrile be 6 parts, the parts by weight of acrylic ester monomer be 10
Part, the parts by weight of organic silicon modified polyurethane are 10 parts；
The parts by weight of the epoxy resin in step 4 are 10 parts, organosilicon/acrylate modified polyurethane
Parts by weight be 40 parts.
Polyalcohol in step one is PPG, preferably polyoxypropyleneglycol, dihydroxy carboxylic acids
For dihydromethyl propionic acid.Organic amine in step 2 is triethylamine, and silane coupler is KH550, binary
Amine is ethylenediamine.Step 3 acrylic ester monomer is acrylic acid AA.Epoxy resin in step 4 is
E-51 bisphenol A epoxide resin.The molecular weight of the polyalcohol in step one between 1000 to 3000,
Chain extender is the low-molecular-weight polyhydroxylated compound that molecular weight is less than 400, preferably dihydroxy ketone.
Embodiment two:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyalcohol in described step one are 40 parts, the parts by weight of diisocyanate are 6
Part, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 50 parts and chain extender be 25 parts, 2,2-double hydroxyls
The parts by weight of methylpropanoic acid are 2.5 parts, the parts by weight of acetone are 25 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 40 parts, the parts by weight of organic amine
Be 50 parts, the parts by weight of silane coupler be 3.5 parts, the parts by weight of deionized water be 30 parts and
The parts by weight of diamine are 30 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 13 parts, the weight of deionized water
Number is 40, the parts by weight of azodiisobutyronitrile are 6.5 parts, the parts by weight of acrylic ester monomer
Be 15 parts, the parts by weight of organic silicon modified polyurethane be 20 parts；
The parts by weight of the epoxy resin in described step 4 are 15 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 45 parts.
Polyalcohol in step one is polyester diol, and dihydroxy carboxylic acids is dimethylolpropionic acid.Step 2
In organic amine be N, N-dimethylethanolamine, silane coupler be selected from KH602, diamine be oneself two
Amine.Epoxy resin in step 4 is E-44 bisphenol A epoxide resin.Step 3 acrylic ester monomer
For methyl acrylate MA.
Embodiment three:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyalcohol in step one are 50 parts, the parts by weight of diisocyanate are 9 parts,
The parts by weight of dihydroxy carboxylic acids be the parts by weight of 60 parts and chain extender be 35 parts, 2,2-double methylols
The parts by weight of propionic acid are 3 parts, the parts by weight of acetone are 35 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 50 parts, the parts by weight of organic amine
Be 60 parts, the parts by weight of silane coupler be 3.8 parts, the parts by weight of deionized water be 40 parts and
The parts by weight of diamine are 35 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 18 parts, the weight of deionized water
Number is 50, the parts by weight of azodiisobutyronitrile are 7.5 parts, the parts by weight of acrylic ester monomer
Be 25 parts, the parts by weight of organic silicon modified polyurethane be 40 parts；
The parts by weight of the epoxy resin in described step 4 are 25 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 55 parts.
Polyalcohol in step one is polyester diol.Silane coupler in step 2 is selected from KH792,
Diamine is selected from IPD.Epoxy resin in step 4 is selected from E-42 bisphenol A epoxide resin.
Embodiment four:
The present embodiment differs primarily in that with embodiment one:
The parts by weight of the polyalcohol in described step one are 60 parts, the parts by weight of diisocyanate are
10 parts, the parts by weight of dihydroxy carboxylic acids be the parts by weight of 70 parts and chain extender be 40 parts, 2,2-is double
The parts by weight of hydroxymethyl propionic acid are 4 parts, the parts by weight of acetone are 40 parts；
The parts by weight of the base polyurethane prepolymer for use as in described step 2 are 60 parts, the parts by weight of organic amine
Be 70 parts, the parts by weight of silane coupler be 4 parts, the parts by weight of deionized water be 50 parts and two
The parts by weight of unit's amine are 40 parts；
The parts by weight of the lauryl sodium sulfate in described step 3 are 20 parts, the weight of deionized water
Number is 60, the parts by weight of azodiisobutyronitrile are 8 parts, the parts by weight of acrylic ester monomer are
30 parts, the parts by weight of organic silicon modified polyurethane be 50 parts；
The parts by weight of the epoxy resin in described step 4 are 30 parts, and organosilicon/acrylate modification gathers
The parts by weight of urethane are 60 parts.
Organosilicon/acrylate embodiment 1-4 obtained/epoxy resin modification polyurethane carries out performance
Test, wherein, control group is the polyurethane without organosilicon/acrylate/epoxy resin modification, examination knot
Fruit is as shown in table 1:
Organosilicon/acrylate embodiment 1-4 obtained/epoxy resin modification polyurethane is sprayed on respectively
On sample, quantity for spray is 240g/m2, pressing 2min, tested after 48 hours.Wherein, sample
Can be knitted fabric, woven fabric or non-woven fabrics, control group be without surveying organosilicon/acrylate/asphalt mixtures modified by epoxy resin
The sample of the polyurethane coating that fat is modified, test result is as shown in table 2.
As can be seen from Table 1 and Table 2, compared with the polyurethane of non-modified, through organosilicon, propylene
The most modified polyurethane of acid esters, epoxy resin have preferable flexibility, resistance to water, mechanical property,
Stability and caking property.By organosilicon/acrylate/epoxy resin modification polyurethane-coated knitted fabric,
After on the sample such as woven fabric or non-woven fabrics, the various performances of the sample after coating are unmodified relative to coating
The sample of polyurethane improved, specifically, the feel of coated product is more soft, and water resistance is more
By force, ultimate strength increase, adhesive fastness more preferable.
The a series of detailed description of those listed above is only for the feasibility embodiment of the present invention
Illustrate, they also are not used to limit the scope of the invention, all without departing from skill of the present invention essence
Equivalent implementations or change that god is made should be included within the scope of the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, but the most each reality
Mode of executing only comprises an independent technical scheme, and this narrating mode of specification is only for understand
Seeing, those skilled in the art should be using specification as an entirety, and the technical scheme in each embodiment is also
Other embodiments that it will be appreciated by those skilled in the art that can be formed through appropriately combined.
Claims (5)
1. the preparation method of a modified polyurethane, it is characterised in that include following operating procedure:
Step one: be 50 parts of polyalcohols, 9 parts of diisocyanate, 60 parts of dihydroxy carboxylics by parts by weight
Acid and 35 parts of chain extenders are put in reactor under a nitrogen atmosphere, and reaction temperature is 70 DEG C～90 DEG C, reaction
Time is 2～4h；Continue to put into the double hydroxymethyl propionic acid of 3 parts of 2,2-in a kettle., 35 parts of acetone expand
Chain end capping reaction, reaction temperature is 50 DEG C～80 DEG C, and the reaction time is 2.5～4.5h, prepares polyurethane pre-
Aggressiveness；
Step 2: be that 50 parts of base polyurethane prepolymer for use as cool to 45 DEG C by the parts by weight obtained in step one
Hereinafter, add under stirring in 60 parts of organic amines with become salt, sequentially add 3.8 parts silane coupled
Agent, 40 parts of deionized waters and 35 parts of diamines, stirring reaction 25～45min, prepare organic-silicon-modified poly-
Urethane；
Step 3: be that 18 parts of lauryl sodium sulfate are dissolved in as aqueous phase in deionized water using parts by weight,
7.5 parts of azodiisobutyronitriles are dissolved in as oil phase in 25 parts of acrylic ester monomers, by aqueous phase and oil phase
In the 40 parts of organic silicon modified polyurethanes being added sequentially in step 2, stirring, then in condition of nitrogen gas
Under be warming up to 70 DEG C～90 DEG C, react 5～6h, obtain organosilicon/acrylate modified polyurethane；
Step 4: 55 parts of organosilicon/acrylate modifications that 25 parts of epoxy resin add in step 3 are gathered
In urethane, stirring, heating water bath, reaction temperature is 80 DEG C～90 DEG C, and the reaction time is 1～2h.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the epoxy resin in described step 4 is selected from E-51 or E-44 or E-42 bis-phenol
A epoxy resin.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the molecular weight of the polyalcohol in described step one is between 1000 to 3000.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the dihydroxy carboxylic acids in described step one is dihydromethyl propionic acid or dihydroxymethyl
Butyric acid.
The preparation of organosilicon/acrylate the most according to claim 1/epoxy resin modification polyurethane
Method, it is characterised in that the chain extender in described step one be molecular weight be less than 400 low-molecular-weight many
Hydroxy compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610476138.8A CN105860085A (en) | 2016-06-24 | 2016-06-24 | Method for preparing modified polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610476138.8A CN105860085A (en) | 2016-06-24 | 2016-06-24 | Method for preparing modified polyurethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105860085A true CN105860085A (en) | 2016-08-17 |
Family
ID=56655710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610476138.8A Pending CN105860085A (en) | 2016-06-24 | 2016-06-24 | Method for preparing modified polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105860085A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589248A (en) * | 2016-12-10 | 2017-04-26 | 白才蓉 | Epoxy resin modified polyurethane-acrylate emulsion and preparation method thereof |
| CN106916254A (en) * | 2017-03-22 | 2017-07-04 | 中山市千佑化学材料有限公司 | Polymerization of acrylic modified polyurethane emulsion and preparation method thereof |
| CN117700670A (en) * | 2023-12-13 | 2024-03-15 | 奥创特新(苏州)科技有限公司 | Preparation method of polyurethane modified tough epoxy resin composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408537A (en) * | 2011-09-19 | 2012-04-11 | 福建宝利特新材料科技有限公司 | A kind of preparation method of acrylate-modified aqueous polyurethane emulsion for synthetic leather |
| CN105218752A (en) * | 2015-09-14 | 2016-01-06 | 江苏龙昇高分子材料科技有限公司 | The preparation method of the polyurethane-acrylate water dispersion of epoxy-silicone resin modification and water-based epoxy zinc-rich primer |
| CN105461863A (en) * | 2015-12-23 | 2016-04-06 | 中山大学惠州研究院 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
-
2016
- 2016-06-24 CN CN201610476138.8A patent/CN105860085A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408537A (en) * | 2011-09-19 | 2012-04-11 | 福建宝利特新材料科技有限公司 | A kind of preparation method of acrylate-modified aqueous polyurethane emulsion for synthetic leather |
| CN105218752A (en) * | 2015-09-14 | 2016-01-06 | 江苏龙昇高分子材料科技有限公司 | The preparation method of the polyurethane-acrylate water dispersion of epoxy-silicone resin modification and water-based epoxy zinc-rich primer |
| CN105461863A (en) * | 2015-12-23 | 2016-04-06 | 中山大学惠州研究院 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589248A (en) * | 2016-12-10 | 2017-04-26 | 白才蓉 | Epoxy resin modified polyurethane-acrylate emulsion and preparation method thereof |
| CN106916254A (en) * | 2017-03-22 | 2017-07-04 | 中山市千佑化学材料有限公司 | Polymerization of acrylic modified polyurethane emulsion and preparation method thereof |
| CN117700670A (en) * | 2023-12-13 | 2024-03-15 | 奥创特新(苏州)科技有限公司 | Preparation method of polyurethane modified tough epoxy resin composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105859978A (en) | Preparation method of organosilicon/acrylic ester modified polyurethane | |
| US9045666B2 (en) | Water-dispersible polyurethane polymer | |
| CN107556483B (en) | Linear amphoteric carboxyl-terminated polyether amino silicone oil, cross-linked amphoteric carboxyl-terminated polyether amino silicone emulsion softening agent prepared from same and preparation method | |
| CN103739818B (en) | Water-borne polyurethane-acrylate emulsion and its preparation method and application | |
| CN105062403A (en) | Synthetic leather binding agent and preparation method thereof | |
| CN105601876B (en) | A kind of cation aqueous polyurethane resin and preparation method thereof | |
| CN105131239A (en) | Water resistance solvent-free polyurethane emulsion and preparation method thereof | |
| CN103073692A (en) | Producing method of water-base polyurethane | |
| CN104611933B (en) | A kind of preparation method of high hydrostatic pressure resistance Waterborne Polyurethane Fabric Coatings | |
| CN105860085A (en) | Method for preparing modified polyurethane | |
| CN111217992B (en) | Polyester polyol and moisture-curing polyurethane hot melt adhesive prepared from same | |
| CN105859977A (en) | Preparation method of organosilicon/acrylic ester/epoxy resin modified polyurethane | |
| CN109734871A (en) | A kind of low water absorbable, high solids content polyaminoester emulsion preparation method | |
| CN106008893B (en) | Polyurethane water-proof endures with all one's will the preparation method and products thereof of agent emulsion | |
| CN1355267A (en) | Water-soluble polyurethane latex adhesive with porous network formed by 'core-shell' structure | |
| CN107151520B (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
| CN106008988A (en) | Preparation method of polypropylene-based modified polyurethane composite material | |
| CN102942893B (en) | Nano modified polyurethane adhesive and preparation method thereof | |
| CN106380568B (en) | Aqueous polyurethane and preparation method thereof and aqueous polyurethane leather filler | |
| CN114106280B (en) | Aliphatic polyurethane resin and preparation method and application thereof | |
| CN107629188A (en) | A kind of preparation method of combination property high-environmental type modified aqueous polyurethane | |
| CN108178822A (en) | A kind of preparation method of environment-friendly modified aqueous polyurethane | |
| CN107857869B (en) | Aqueous polyurethane and its preparation method and application | |
| CN108727552B (en) | Full-bio-based emulsifier and preparation method and application thereof | |
| JPS58219213A (en) | Aqueous dispersion of polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160817 |
|
| WD01 | Invention patent application deemed withdrawn after publication |