CN106589286A - Silane modified polyurethane resin and preparation method thereof - Google Patents
Silane modified polyurethane resin and preparation method thereof Download PDFInfo
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- CN106589286A CN106589286A CN201611038096.6A CN201611038096A CN106589286A CN 106589286 A CN106589286 A CN 106589286A CN 201611038096 A CN201611038096 A CN 201611038096A CN 106589286 A CN106589286 A CN 106589286A
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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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
Abstract
The invention provides silane modified polyurethane resin and a preparation method thereof. The resin is prepared by reaction of the following raw materials: (a) a polyisocyanate; (b) a component which comprises (b1) poly(methyl)acrylate containing a NCO reactive group and /or (b2) a polyol; (c) a silane coupling agent; (d) a component which comprises (d1) poly(methyl)acrylate containing a NCO reactive group and /or (d2) a polyol; and the raw materials contain at least one of the (b1) and the (d1). Through introduction of a poly(methyl)acrylate structure onto a branched chain and/or the main chain of the silane modified polyurethane resin, the hydrocarbon medium resistance and weather resistance of the silane modified polyurethane resin are greatly improved; and siloxy for improving polyurethane water resistance and heat resistance is introduced. The silane modified polyurethane resin solves the problems of poor mechanical strength and hydrocarbon medium resistance of the resin.
Description
Technical field
The present invention relates to a kind of silicane-modified polyurethane resin, and in particular to one kind contains poly- (methyl) acrylate structural
Silicane-modified polyurethane resin.
Background technology
The characteristics of polyurethane has big, wear-resisting adhesive strength, big mechanical strength and good vibration absorption, gluing
Agent, fluid sealant, elastomer field are all widely used.But due to there is free isocyanate, and heat-resisting, water resistance compared with
Weak the features such as, limit polyurethane body and tie up to and apply in more fields.Silicane-modified polyurethane is developed based on problem above
System.
Silicane-modified polyurethane (SPUR) is that the terminal isocyanate group of polyurethane prepolymer is become silane oxygen by reaction
Base, main chain is polyurethanes segment.The silicone segments for introducing low pole and high bond energy cause silane end capped polyurethane
Resistance to water, heat resistance all make moderate progress.Silane end capped polyurethane can be used as one-component silane end capped polyurethane fluid sealant, viscous
Knot agent.
CN103910847A discloses a kind of preparation method of silicane-modified polyurethane oligomer, and the polyurethane for thus preparing is close
Sealing is limited by technique, have selected the polyethers or polyester of relatively low degree of functionality as raw material.This can substantially sacrifice the machinery of polyurethane
Intensity, and the introducing of silicone segments can not still be effectively improved destruction of the resistance to hydrocarbon medium of polyurethane to material.
CN1865313A is provided a kind of hydroxy acrylate and is present on a small quantity in silicane-modified polyurethane with block form
Process for preparing resins, its silane coupler is dihydroxylic alcohols, is present in resinous polymer as chain extender, is solved to a certain extent
The problem of polyurethane acrylate resin heat resistance and the resistance to water of having determined, but operating procedure is complex, and raw material is limited relatively tighter
Weight, increased the difficulty for using.System still be NCO group terminated polymer, increased resin preservation difficulty, and due to
The presence of free isocyanate cannot be avoided, and limit its application in low bio-toxicity field.
It is aqueous poly- to improve with polyacrylate blending that CN101429407A provides a kind of organic silicon modified aqueous polyurethane
The method that urethane resistance to water and weatherability are not enough.The performance deficiency of aqueous polyurethane, the party are solved by the mode of physical entanglement
Method is easy to use, but improvement is general, and the process being blended needs the presence of solvent, this feature of environmental protection with aqueous polyurethane
Can conflict.
The technical scheme of above-mentioned patent mainly includes two ways:A small amount of altered contents are introduced in agent structure, or
Material hybridization is carried out using the mode of physical blending.Both modes all can not inherently improve the resistance to hydrocarbon medium of material
Performance.
The content of the invention
It is an object of the invention to provide a kind of silicane-modified polyurethane resin, in polyurethane backbone and/or side-chain structure
It is middle to introduce poly- (methyl) acrylate structural, and the silane epoxide for improving polyurethane resistance to water and heat resistance is introduced, solve tree
The problem of fat bad mechanical strength and resistance to hydrocarbon medium difference.
To reach above technical purpose, the present invention is employed the following technical solutions:
A kind of silicane-modified polyurethane resin, the resin is obtained including following raw material reaction:Based on the weight of resin,
A () polyisocyanates, consumption is 1~40wt%, preferably 5~30wt%;
B () component, contains:
(b1) in per molecule NCO reactive groups number be 1~4, preferably 2~3, and number-average molecular weight be 100
Poly- (methyl) acrylate of~5000g/mol, consumption be 0~60wt%, preferably 10~50wt%,
And/or,
(b2) number-average molecular weight is the polyalcohol of 60~20000g/mol, and consumption is 10~60wt%, preferably 15~
50wt%;
And (b1) and (b2) content and for 10~70wt%, preferably 15~65wt%;
C () silane coupler, consumption is 0.02~40wt%, preferably 1~30wt%;
D () component, contains:
(d1) number of NCO reactive groups is 2~20 in per molecule, preferably 4~10, and number-average molecular weight is
Poly- (methyl) acrylate of 3000~200000g/mol, consumption be 0~80wt%, preferably 20~60wt%,
And/or,
(d2) degree of functionality is 3~10, and number-average molecular weight is the polyalcohol of 500~30000g/mol, consumption is 10~
90wt%, preferably 30~70wt%;
And (d1) and (d2) content and for 15~80wt%, preferably 25~65wt%;
Described raw material is including at least the one kind in (b1) and (d1).
When only (b2) is used in component (b) of the present invention, when not using (b1), the component (d) must use (d1),
But can (d2) use or not use.
The used in amounts of (a) of the present invention, (b) raw material will meet:Contained NCO group is contained with (b) in (a)
The mol ratio 1.5~8 of some NCO reactive groups:1, preferably 2~5:1.
The mol ratio of the NCO group in the NCO reactive groups in (b) of the present invention, (c) and (d) and (a) is
0.7~1.5, preferably 0.9~1.2.
(a) of the present invention polyisocyanates is selected from aliphatic, alicyclic, aromatic series and the araliphatic of NCO degree of functionality >=2
One or more in polyisocyanates and its derivative;The derivative is comprising iminooxadiazinedionepolyisocyanates diketone, isocyanuric acid
Ester, urea diketone (uretdione), carbamate, allophanate, biuret, Niao, oxadiazine triketone, oxazolidones, uride
With the polyisocyanate derivative of one or more in carbodiimide.
The suitable example of (a) of the present invention polyisocyanates has:1,4- fourth diisocyanate, 1,6- oneself two isocyanic acids
Ester (HDI), IPDI (IPDI), 2,2,4- trimethyls-hexamethylene diisocyanate, 2,4,4- trimethyls-
Hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate (H12) and/or its isomer, isocyanatomethyl MDI-
1,8- octane diisocyanates, 1,4- cyclohexane diisocyanates, 1,4- phenylene diisocyanates, 2,4 toluene diisocyanate
And/or 2,6- toluene di-isocyanate(TDI)s (TDI), (the 2- isocyanic acid propyl- 2- ester groups) benzene (TMXDI) of 1,3- bis- and 1,4- bis- (TDI)
(2- isocyanic acid propyl- 2- ester groups) benzene (TMXDI), 1,3- bis- (isocyanatomethyl) benzene (XDI), the isocyanic acid of 2,4- xylenes two
Ester, 1- methyl -2,4- cyclohexane diisocyanates, 1,5- naphthalene diisocyanates, methyl diphenylene diisocyanate, triphenyl first
Alkane -4,4 ', 4 "-triisocyanate;The polyisocyanates can also be with 2 based on the polyisocyanates of above-mentioned example
The above-NCO group and with urea diketone, isocyanuric acid ester, carbamate, allophanate, biuret, iminooxadiazinedionepolyisocyanates
Diketone is He the derivative of/Huo oxadiazine triketone structures.
Preferably, the polyisocyanates is selected from aliphatic, alicyclic, aromatic series and araliphatic diisocyanate
Plant or various, preferably 1, hexamethylene-diisocyanate (HDI), IPDI (IPDI), dicyclohexyl methyl hydride two are different
Cyanate (H12MDI), 1,4- cyclohexane diisocyanates, 1- methyl -2,4- cyclohexane diisocyanates, diphenyl methane two are different
The polyisocyanic acid that cyanate, 1,5- naphthalene diisocyanates and above-mentioned polyisocyanates are modified by carbamate groups
Ester.
The degree of functionality of the polyalcohol in component (b2) of the present invention is 2~3, can be that polyethers, polyester, Merlon are more
First alcohol etc., even 60~20000g/mol of number-average molecular weight, preferably 200~10000g/mol, molecular weight are less than 200g/mol
Small molecule polyol etc..
In component (b2) of the present invention polycarbonate polyol can using have phosgenation, carbon dioxide adjust copolymerization method,
Cyclic carbonate ring-opening polymerisation method or ester-interchange method synthesis are obtained.
Polycarbonate polyol of the present invention preferably carries out ester exchange reaction and synthesizes poly- carbon by dihydroxylic alcohols and carbonic ester
Acid esters polyalcohol.
During ester-interchange method polycarbonate synthesis polyalcohol of the present invention, the dihydroxylic alcohols includes but is not limited to 1,2-
One or more in ethylene glycol, 1,4- butanediols, 1,5- pentanediols and 1,6-HD;Preferably 1,4- butanediols and/or
1,5- pentanediols.The carbonic ester includes but is not limited to dimethyl carbonate and diethyl carbonate;Preferably dimethyl carbonate.
Small molecule polyol of the present invention include ethylene glycol, 1,2- propane diols, 1,3- propane diols, 1,3 butylene glycol, 1,
4- butanediols, 1,5- pentanediols, 1,6-HD, 2,2- dimethyl -1,3- propane diols (neopentyl glycol), 1,4- hexamethylene diformazans
Alcohol, 3- methyl isophthalic acids, 5- pentanediols, 2,4- diethyl -1,5- pentanediols, 2,2,4- trimethyl -1,3- pentanediols, decanediol and ten
One or more in dioxane glycol, glycerine, trimethylolpropane etc..
The degree of functionality of component (d2) polyalcohol of the present invention is 3~10, preferably 3~6, the equal molecule of number of the polyalcohol
Measure as 500~30000, preferably 4000~20000.Component (d2) can be polyethers, PEPA etc..
PPG in (b2) of the present invention and (d2), is by initiator and the ring containing 2~6 carbon atoms
Oxygen compound reacts, the PPG for preparing.The initiator is small molecule polyol, small molecule polyamine and little point
One or more in sub- hydramine;Including but not limited to water, ethylene glycol, propane diols, glycerine, trimethylolpropane, pentaerythrite,
One or more in xylitol, sorbierite, bisphenol-A, ethylenediamine, triethylene diamine and toluenediamine;Preferably water, propane diols
With one or more in glycerine.Described epoxide is preferably in oxirane, expoxy propane and tetrahydrofuran (THF)
One or more.
Preferably, PPG of the present invention is polyethylene glycol, PTMG, tetrahydrofuran-oxygen
Change one or more in ethylene copolymer ether glycol, poly glycol monomethyl ether.
PEPA in (b2) of the present invention and (d2) can be by dihydroxylic alcohols and dicarboxylic acids, acid anhydrides or binary
Carboxylate is esterified or ester exchange reaction is prepared.The dihydroxylic alcohols is in aliphatic dihydroxy alcohol and aromatic diol
One or more, preferred carbon number be 2~12;Including but not limited to ethylene glycol, 1,2- propane diols, 1,3- the third two
Alcohol, 1,3 butylene glycol, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, 2,2- dimethyl -1,3- propane diols (new penta 2
Alcohol), 1,4- cyclohexanedimethanols, 3- methyl isophthalic acids, 5- pentanediols, 2,4- diethyl -1,5- pentanediols, 2,2,4- trimethyl -1,3-
One or more in pentanediol, decanediol and dodecanediol, more preferably ethylene glycol, 1,3-PD, BDO, 1,
5- pentanediols, 1,6-HD etc..The dicarboxylic acids, acid anhydrides or dicarboxylic esters are aliphatic, alicyclic and aromatics binary
One or more in carboxylic acid, acid anhydrides or dicarboxylic esters, preferred carbon number is 4~15;Including but not limited to benzene two
Formic acid, phthalate anhydride, repefral, dimethyl terephthalate (DMT), succinic acid, glutaric acid, adipic acid, heptan two
Acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, M-phthalic acid, terephthalic acid (TPA), cyclohexyl dicarboxylic acid, O-phthalic
One or more in acid anhydrides and tetrabydrophthalic anhydride;More preferably phthalic acid, phthalate anhydride, phthalic acid diformazan
One or more in ester, dimethyl terephthalate (DMT), succinic acid, glutaric acid, adipic acid.
The example of PEPA of the present invention include but is not limited to polyethylene glycol adipate, polyadipate oneself two
Alcohol ester, poly adipate succinic acid ester, poly terephthalic acid hexylene glycol ester, polybutylene terephthalate (PBT), poly terephthalic acid
Propylene glycol ester etc..
Poly- (methyl) acrylate of the present invention can be the small-molecule substance containing carbon-carbon double bond and (methyl) third
The copolymer of olefin(e) acid ester, and in order to obtain poly- (methyl) acrylate containing NCO reactive groups, wherein should also contain (first
Base) (methyl) acrylate containing NCO reactive groups such as hydroxy-ethyl acrylate, methacrylic acid, acrylic acid, acrylamide
At least one monomer, using general radical copolymerization or K.Matyjaszewski in J.Am.Chem.SOC.1995,117,
ATRP (ATRP) method that 5614-5615 is delivered and such as G.Moad are in Macromolecules
The mode of the segment transferring free-radical polymerization (RAFT) of 1998,31,5559-5562 statements obtains polymer.
The example of the small-molecule substance containing carbon-carbon double bond of the present invention has ethene, propylene, isobutene, 1,3- fourths two
The alkene of the carbon-carbon double bonds such as alkene, 1- octenes.
(methyl) acrylate of the present invention includes (methyl) acrylate of saturated alcohols, preferably (methyl) propylene
The ester that acid is formed with the C1-C10 alcohol of saturation.The example of (methyl) acrylate includes but is not limited to (methyl) acrylic acid first
Ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate,
(methyl) n-octyl, (methyl) 2-EHA, 1,2- ethylene glycol two (methyl) acrylate, 1,4- fourths two
Alcohol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and
Pentaerythrite four (methyl) acrylate;It is preferred that (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid are just
One or more in propyl ester, (methyl) n-butyl acrylate.
(methyl) acrylate containing NCO reactive groups of the present invention contains at least one can be with NCO reactions
Active group and at least one (methyl) are acrylate-based.
Preferably, (methyl) acrylate containing NCO reactive groups of the present invention is selected from hydroxy-ethyl acrylate (letter
Be written as HEA), hydroxyethyl methacrylate (being abbreviated as HEMA), hydroxypropyl acrylate (being abbreviated as HPA), tertiary carbonic acid glycidyl
Ester acrylate, acrylic acid 1,3 butylene glycol ester, methacrylic acid 1,3 butylene glycol ester, acrylic acid 1,6-HD ester, methyl
Acrylic acid 1,6-HD ester, acrylic acid DOPCP, methacrylic acid DOPCP, bisphenol A dimethacrylate shrink sweet
Grease, bisphenol-A dimethyl allene acid glycidyl ester, ethylene-oxide-modified bisphenol A dimethacrylate ethylene oxidic ester, epoxy second
Alkane modified bisphenol-A dimethyl allene acid glycidyl ester, trimethylolethane diacrylate, trimethylolethane dimethyl
Acrylate, trimethylolpropane diacrylate, trimethylolpropane dimethylacrylate, the acrylic acid of pentaerythrite three
Ester, pentaerythritol acrylate trimethyl, dipentaerythritol triacrylate, dipentaerythritol trimethyl acrylic ester, two seasons
Penta tetra-acrylate, dipentaerythritol tetramethyl acrylate, Dipentaerythritol Pentaacrylate, the first of dipentaerythritol five
One or more in base acrylate and hydroxyl polyester acrylate oligomers.
It is highly preferred that (methyl) acrylate containing NCO reactive groups of the present invention is selected from hydroxy-ethyl acrylate
(being abbreviated as HEA), hydroxyethyl methacrylate (being abbreviated as HEMA), hydroxypropyl acrylate (being abbreviated as HPA), versatic acid shrink sweet
Grease acrylate, pentaerythritol triacrylate (being abbreviated as PETA), trimethylolpropane diacrylate and two seasons penta 4
One or more in the acrylate of alcohol five.
Small-molecule substance, (methyl) acrylic acid of carbon-carbon double bond in the raw material of poly- (methyl) acrylate of the present invention
The mol ratio of ester and (methyl) acrylate containing NCO reactive groups is 0~60:50~100:1~50, preferably 0~40:
60~90:1~30.
Component (c) silane coupler of the present invention includes silicon of the end group for sulfydryl, primary amino radical, secondary amino group or epoxy radicals
One or more in alkane coupling agent.
It is of the present invention containing end sulfydryl silane coupler example include but is not limited to γ-mercapto propyl trimethoxy alkane,
Gamma-mercaptopropyltriethoxysilane etc..
The example of the silane coupler of the primary amino radical containing end of the present invention or secondary amino group includes but is not limited to gamma-amino propyl group
Trimethoxy silane, γ aminopropyltriethoxy silane, gamma-amino hydroxypropyl methyl dimethoxysilane, gamma-amino propyl group
Methyldiethoxysilane, gamma-amino dimethylamine methoxylsilane, gamma-amino propyl-dimethyl Ethoxysilane, N- β
(aminoethyl)-γ-aminopropyltrimethoxysilane, anilinomethyl trimethoxy silane, anilinomethyl triethoxysilane, N- first
Base γ-aminopropyltrimethoxysilane, N- (normal-butyl)-γ-aminopropyltrimethoxysilane, N- (cyclohexyl)-γ-aminopropyl
Trimethoxy silane etc..
It is of the present invention to include but is not limited to γ-(oxygen of 2,3- epoxies third) propyl group front three containing epoxy terminated silane coupler
TMOS, γ-(oxygen of 2,3- epoxies third) propyl-triethoxysilicane, γ-(oxygen of 2,3- epoxies third) hydroxypropyl methyl dimethoxy
Silane or γ-(oxygen of 2,3- epoxies third) hydroxypropyl methyl diethoxy silane etc..
Silane coupler of the present invention preferably is selected from γ-mercapto propyl trimethoxy alkane, γ-mercapto propyl-triethoxysilicane
Alkane, γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy
Silane, anilinomethyl trimethoxy silane, anilinomethyl triethoxysilane, N- methyl γ-aminopropyltrimethoxysilanes, N-
One kind or many in (normal-butyl)-γ-aminopropyltrimethoxysilane and N- (cyclohexyl)-γ-aminopropyltrimethoxysilane
Kind.
The present invention also provides a kind of method for preparing the silicane-modified polyurethane resin, comprises the following steps:
Proportionally,
(1) component (b) and the reaction of (a) polyisocyanates are prepared into performed polymer;
(2) step (1) gained performed polymer reacts with (c) silane coupler, obtains part by silane epoxide terminated prepolymer;
(3) step (2) gained part is reacted by silane epoxide terminated prepolymer and component (d), is obtained described silane-modified
Polyurethane resin.
NCO group contained in performed polymer and the NCO reactions contained by (c) silane coupler in step (2) of the present invention
Property group mol ratio be 1:0.1~0.8, preferably 1:0.3~0.7.
Optional catalyst and optional solvent using catalysis polyurethane reaction in method of the present invention.Such as
Fruit uses solvent, after the completion of end reaction, using method well known in the art by solvent removal.
Catalyst of the present invention includes one or more in tertiary amine catalyst and organometallic catalysts.
Tertiary amine catalyst of the present invention includes pentamethyl-diethylenetriamine, pentamethyldipropylenetriamine, N- first
Base imidazoles, DMIZ 1,2 dimethylimidazole, N, N- dimethyl cyclohexyl amines, N- methyldicyclohexylamines, triethylene diamine, N-methylmorpholine,
N-ethylmorpholine, N- cyclohexyl morpholines, triethylamine, tri-n-butylamine, 1,4- lupetazins, N, N- dimethyl benzylamines, N, N- diformazans
Base (cetyl) amine, two (dimethylaminoethyl) ethers, N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-tetramethyl the third two
Amine, N, N, N ', N '-tetramethyl butane diamine, N, N, N ', N ' -4-methyl hexamethylene diamine, N, N, N ', the N '-hexamethylene of tetramethyl diaminourea two
Methylmethane, triethanolamine, triisopropanolamine, three (dimethylamino-propyl) amine, N methyldiethanol amine, N- ethyldiethanolamines,
In dimethylaminoethoxyethanol, trimethyl hydroxyethylammonium propane diamine, trimethyl hydroxyethylammonium ethylenediamine and dimethylethanolamine one
Plant or various;It is preferred that triethylene diamine, two (dimethylaminoethyl) ethers, N, N- dimethyl cyclohexyl amines, pentamethyl-diethylenetriamine,
Pentamethyldipropylenetriamine, N- methyldicyclohexylamines, N, N, N ', N ' -4-methyl hexamethylene diamine, N, N, N ', N '-tetramethyl the third two
Amine, three (dimethylamino-propyl) amine, N, N- dimethyl benzylamines, N, N- dimethyl (cetyl) amine, dimethylethanolamine, diformazan
Aminoethoxyethanol, trimethyl hydroxyethylammonium propane diamine, trimethyl hydroxyethylammonium ethylenediamine, N-methylmorpholine, N-ethylmorpholine and
One or more in triethylamine.
Organometallic catalysts of the present invention, such as organic potassium compound, organo-tin compound, such as organic carboxyl acid
Tin (II) salt, such as oxalic acid tin (II), two tin octoates (II), two (ethyl) caproic acid tin (II) and tin dilaurate tin (II), and
Dialkyl tin (IV) salt of organic carboxyl acid, such as dibutyltin diacetate, dibutyl tin laurate, dibutyitin maleate and two
Acetic acid dioctyl tin.Other very applicable compounds are dialkyl tin (IV) sulfhydryl compounds, such as the sulphur of dilauryl tin (IV) two
Alkoxide, and general formula R2Sn(SR′-O-CO-R″)2Or R2Sn(SR′-CO-OR″)2Compound, in formula R be at least 8 carbon
The alkyl of atom, R ' is the alkyl of at least 2 carbon atoms, and R is " for the alkyl of at least 4 carbon atoms.
The example of this kind of catalyst is such as the catalyst disclosed in DD-A-218668:(the 2- ethyl hexyls of dioctyl tin-two
Sour THIOGLYCOL ester), dioctyl tin-two (laurate THIOGLYCOL ester), dioctyl tin-two (thiol acid group close acetic acid 2-
Ethylhexyl), dioctyl tin-two (thiol acid group close hexyl acetate) and (the thiol acid group conjunction acetic acid bay of dioctyl tin-two
Ester).Other very applicable catalyst are the formula (R as disclosed in DD-A-2555353Sn)2O、R2SnS、(R3Sn)2S、R2Sn、
(SR′)2Or RSn (SR ')3The organo-tin compound for having tin-oxygen or a tin-sulfide linkage, in formula R and R ' for have 4~8 carbon atoms (
In the case of R) and 4~12 carbon atoms (in the case of R '), it is have 1 that R ' is alternatively-R " COO R " or-R " COOR, wherein R "
The alkyl of~6 carbon atoms, R is the alkylidene for having 4~12 carbon atoms.The example that can be mentioned that is:Two (tributyl tins) are aoxidized
Thing, dibutyl tin sulfide, dioctyl tin sulfide, two (tributyl tin) sulfide, dibutyl tin-(thio Glycolic acid 2- second
The own ester of base), dioctyl tin-two (thio Glycolic acid 2- Octyl Nitrites), tin octylate-three (thio Glycolic acid 2- Octyl Nitrites), two
Tin octylate-two (2 ethyl hexanoic acid THIOGLYCOL ester) and dibutyl tin-two (laurate THIOGLYCOL ester).
The example of suitable organic potassium compound includes but is not limited to isooctyl acid potassium, potassium acetate, potassium oleate etc..
The example of suitable organometallic catalysts can also be other organo-metallic compounds, such as butyl titanate,
Zinc Isoocatanoate etc..
Organo-metallic compound can be used alone as catalyst or be used in the form of carbon monoxide-olefin polymeric.
Organometallic catalysts of the present invention preferably include isooctyl acid potassium, potassium acetate, dibutyl tin laurate,
One or more in butyl titanate, zinc Isoocatanoate, stannous octoate and potassium oleate.
All solvents generally used in polyurethane chemistry can be used as above-mentioned solvent.Particularly ester, ketone, halo
Hydrocarbon compound, alkane, olefine and aromatic compound.The example of these solvents be as dichloromethane, trichloro ethylene, toluene,
Dimethylbenzene, butyl acetate, pentyl acetate, isobutyl acetate, methyl iso-butyl ketone (MIBK), methoxy butyl acetate, hexamethylene, cyclohexene
Ketone, dichlorobenzene, metacetone, DIBK, dioxane, ethyl acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol
Single ethylhexoate, acetic acid 2- ethylhexyls, ethylene diacetate, heptane, hexane, Sucrose Acetate base ester, isooctane, second
One or more in sour isopropyl esters, acetone, MEK, tetrahydrofuran or tetrachloro-ethylene etc..
It has been desirable in certain applications, considering that the viscosity of silicane-modified polyurethane resin is excessive, step (1)~(2) can be obtained
Part by silane epoxide terminated prepolymer as component A, by (d) component as B component, component A and B component are individually stored up
Deposit, used in double-component form.Optional auxiliary agent well known in the art can be added in the component A, B component.It is described
Auxiliary agent includes but is not limited to filler, plasticizer etc., the example of described filler include flake asbestos, silica white, phenolic resin, porcelain powder,
Titanium dioxide, alumina powder, graphite powder, kaolin powder, curing aluminium powder, carbon black, White Carbon black, organobentonite, polyamide, work
Property calcium, talcum powder etc.;The example of the plasticizer includes diisooctyl phthalate, dioctyl phthalate, adjacent benzene two
Formic acid dibutyl ester, benzyl phthalate, diisononyl phthalate, diisooctyl phthalate, 2,2,4- trimethyls-
1,3- pentanediols double isobutyrate, ATBC, 1,2- cyclohexane diacid dinonyls etc.;Can also will be described
During catalyst is added to A or B component as curing accelerator.
Silicane-modified polyurethane resin of the present invention can be resistant to hydrocarbon medium, require more than GB/T 539-2008, increase
Rate again<30%th, rate 0~20% is thickened.
Hydrocarbon medium of the present invention includes oil deep processed product, such as gasoline, kerosene, diesel oil, lubricating oil, pitch, each
Plant solvent naphtha etc..
Silicane-modified polyurethane resin of the present invention, has been carried out organic using the intrinsic advantage of multiple polymers material
Combination, realizes diversity functionally and complexity, and a certain proportion of poly- (first is particularly introduced on main chain and/or side chain
Base) acrylate makes the resistance to hydrocarbon medium performance of material be improved;In addition, when the main chain and side chain of resin material are all introduced
Poly- (methyl) acrylate, its resistance to hydrocarbon medium performance and weather resistance are greatly improved;The present invention is raw materials used to be easy to get,
Synthesis technique is simple, is not susceptible to uncontrollable reaction;And can be adjusted by simple proportioning or feeding sequence change
Realize extensive adjustable in material behavior.
Specific embodiment
Thicken rate, rate of body weight gain and refer to GB3912-1983, Mechanics Performance Testing refers to GB/T 528-2009.
Embodiment one
The preparation of silicane-modified polyurethane performed polymer:It is 2000 by 400g number-average molecular weights2056 (ten thousand is magnificent
Chemistry) and 133.2g IPDI be added in 5L three-neck flasks, be preheating to 50-60 DEG C while stirring, addition 0.1g stannous octoates are urged
Agent reacts 2h after 60 DEG C, is subsequently adding 117.6g γ-mercaptopropyl trimethoxysilane and continues to react 1h, is obtained silane-modified
Base polyurethane prepolymer for use as.
Polymethacrylates (degree of functionality=5.4 for adding in system afterwards;Number-average molecular weight=9300g/mol;
Glass transition temperature=- 5 DEG C;Methyl methacrylate/styrene/acrylic butyl ester/hydroxyethyl methacrylate mol ratio
=1:0.3:2:1.3 are prepared using radical polymerization) mixed solution of 344.4g and DMF 2L, reacts 2h
Afterwards, heating in vacuum desolvation.
Above-mentioned silicane-modified polyurethane is poured into into the thick films of 2mm, in 23 DEG C of temperature, under conditions of humidity 50%, solidification
21 days, obtain bubble-free homogeneous membrane.Surface drying time is 3h, does solid work time 13h.The tensile strength of film be 15MPa, extension at break
Rate is 411%;After American Standard Test oil (IRM903) immersion 72h, rate=5%, rate of body weight gain=7%, tensile strength are thickened
13MPa, elongation at break 452%.
Embodiment two
The preparation of silicane-modified polyurethane performed polymer:By 200g polycarbonate polyols (Asahi Chemical Industry;T5651, the equal molecule of number
Measure as 1000g/mol, degree of functionality=2), 200g polymethacrylates (degree of functionality=2.1;Number-average molecular weight=2000, glass
Change transition temperature=- 23 DEG C;The different monooctyl ester of methyl methacrylate/acrylic acid/hydroxyethyl methacrylate mol ratio=1:2.7:
1.2 using radical polymerization prepare) and 116.7g TDI be added in 3L three-neck flasks, while stirring preheat 50-60 DEG C, addition
0.1g stannous octoate catalysts react 2h after 60 DEG C, are subsequently adding 158g anilinomethyl triethoxysilanes and continue to react 1h,
Prepared silicane-modified polyurethane performed polymer.
Add 400g PPG (Gaoqiao Petrochemical Companies in system afterwards;GEP-828, number-average molecular weight 6000, sense
Degree=3) and acetone 200mL, continue to react 5h.
Above-mentioned silicane-modified polyurethane is poured into into the thick films of 2mm, in 23 DEG C of temperature, under conditions of humidity 50%, solidification 7
My god, obtain bubble-free homogeneous membrane.Surface drying time is 5h, does solid work time 20h.The tensile strength of film be 5.2MPa, extension at break
Rate is 370%;After American Standard Test oil (IRM903) immersion 72h, rate=4%, rate of body weight gain=5%, tensile strength are thickened
2.9MPa, elongation at break 390%.
Embodiment three
The preparation of silicane-modified polyurethane performed polymer:By 400g polymethacrylates (degree of functionality=2.1;The equal molecule of number
Amount=4000g/mol, glass transition temperature=- 8 DEG C;Different monooctyl ester/butyl acrylate/the first of methyl methacrylate/acrylic acid
Base hydroxy-ethyl acrylate mol ratio=1:1.3:1.8:1 is prepared using radical polymerization) and be added to the necks of 5L tri- and burn with 150gMDI
In bottle, 50-60 DEG C is preheating to while stirring, adds 0.1g neodecanoic acids tin catalyst to react 2h after 60 DEG C, be subsequently adding 165g
Cyclohexylamine MTES continues to react 1h, and silicane-modified polyurethane performed polymer is obtained.
Add 1600g polymethacrylates (degree of functionality=5 in system afterwards;Number-average molecular weight=20000g/
mol;Glass transition temperature=- 17 DEG C;EMA/butyl acrylate/Isooctyl acrylate monomer/hydroxyethyl methacrylate
Ethyl ester mol ratio=1:1.5:1.3:1.3 are prepared using ATRP) and N,N-dimethylformamide 2L's is molten
Liquid, after reaction 2h, heating in vacuum desolvation.
Above-mentioned silicane-modified polyurethane is poured into into the thick films of 2mm, in 25 DEG C of temperature, under conditions of humidity 50%, solidification 7
My god, obtain bubble-free homogeneous membrane.Surface drying time is 5h, does solid work time 20h.The tensile strength of film be 4.9MPa, extension at break
Rate is 479%;After American Standard Test oil (IRM903) immersion 72h, rate=3%, rate of body weight gain=3%, tensile strength are thickened
4.8MPa, elongation at break 512%.
Example IV
The preparation of silicane-modified polyurethane performed polymer:By polyester diol that 200g number-average molecular weights are 1000 (PN-110) it is added in 5L three-neck flasks with 126g 1,5- naphthalene diisocyanate, 50- is preheating to while stirring
60 DEG C, add 0.1g stannous octoate catalysts to react 2h after 60 DEG C, be subsequently adding 89.5g γ-aminopropyltrimethoxysilanes
Continue to react 1h, silicane-modified polyurethane performed polymer is obtained.
Add polymethacrylates (degree of functionality=5.4 in system afterwards;Number-average molecular weight=9300g/mol;Glass
Glass transition temperature=- 6 DEG C;Methyl methacrylate/butyl acrylate/hydroxyethyl methacrylate mol ratio=1:2:1.3
Prepared using radical polymerization) mixed solution of 516.7g and DMF 3L, after reaction 2h, heating in vacuum removing
Solvent.
Above-mentioned silicane-modified polyurethane is poured into into the thick films of 2mm, in 23 DEG C of temperature, under conditions of humidity 50%, solidification
21 days, obtain bubble-free homogeneous membrane.Surface drying time is 3h, does solid work time 13h.The tensile strength of film be 25MPa, extension at break
Rate is 394%;After American Standard Test oil (IRM903) immersion 72h, rate=4%, rate of body weight gain=6%, tensile strength are thickened
23MPa, elongation at break 352%.
Comparative example
The preparation of silicane-modified polyurethane performed polymer:By the polycarbonate polyol (rising sun that 200g number-average molecular weights are 1000
Chemical conversion;T5651, number-average molecular weight is 1000g/mol, degree of functionality=2) be added in 5L three-neck flasks with 150gMDI, side stirring
While being preheating to 50-60 DEG C, add 0.1g stannous octoate catalysts to react 2h after 60 DEG C, be subsequently adding the second of 110g anilinomethyls three
TMOS continues to react 1h, and silicane-modified polyurethane performed polymer is obtained.
Add 650g in system afterwards3135 (number-average molecular weight is 5000g/mol, degree of functionality=3)
With the mixed solution of DMF 2L, after reaction 2h, heating in vacuum desolvation.
Above-mentioned silicane-modified polyurethane is poured into into the thick films of 2mm, in 23 DEG C of temperature, under conditions of humidity 50%, solidification
21 days, obtain bubble-free homogeneous membrane.Surface drying time is 2.5h, does solid work time 12h.The tensile strength of film is 13MPa, and fracture is stretched
Long rate is 611%;After American Standard Test oil (IRM903) immersion 72h, rate=50% is thickened, rate of body weight gain=57%, stretching is strong
Degree 3MPa, elongation at break 60%.
Claims (9)
1. a kind of silicane-modified polyurethane resin, the resin is obtained including following raw material reaction:Based on the weight of resin,
A () polyisocyanates, consumption is 1~40wt%, preferably 5~30wt%;
B () component, contains:
(b1) in per molecule NCO reactive groups number be 1~4, preferably 2~3, and number-average molecular weight be 100~
Poly- (methyl) acrylate of 5000g/mol, consumption be 0~60wt%, preferably 10~50wt%,
And/or,
(b2) number-average molecular weight is the polyalcohol of 60~20000g/mol, and consumption is 10~60wt%, preferably 15~50wt%;
And (b1) and (b2) content and for 10~70wt%, preferably 15~65wt%;
C () silane coupler, consumption is 0.02~40wt%, preferably 1~30wt%;
D () component, contains:
(d1) in per molecule NCO reactive groups number be 2~20, preferably 4~10, and number-average molecular weight be 3000~
Poly- (methyl) acrylate of 200000g/mol, consumption be 0~80wt%, preferably 20~60wt%,
And/or,
(d2) degree of functionality is 3~10, and number-average molecular weight is the polyalcohol of 500~30000g/mol, and consumption is 10~90wt%, excellent
Select 30~70wt%;
And (d1) and (d2) content and for 15~80wt%, preferably 25~65wt%;
Described raw material is including at least the one kind in (b1) and (d1).
2. the resin in reacting according to claim 1, it is characterised in that contained NCO group and institute in (b) in (a)
The mol ratio 1.5~8 of the NCO reactive groups for containing:1, preferably 2~5:1;NCO reactions in described (b), (c) and (d)
Property group and (a) in the mol ratio of contained NCO group be 0.7~1.5, preferably 0.9~1.2.
3. resin according to claim 1 and 2, it is characterised in that (a) polyisocyanates is selected from NCO degree of functionality >=2
Aliphatic, alicyclic, aromatic series and araliphatic polyisocyanate and its derivative in one or more;It is preferred that 1,6- oneself two
Isocyanates, IPDI, dicyclohexyl methyl hydride diisocyanate, 1,4- cyclohexane diisocyanates, 1- first
Base -2,4- cyclohexane diisocyanates, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates and the polyisocyanate
Cyanate is by one or more in the modified polyisocyanates of carbamate groups.
4. the resin according to any one of claim 1-3, it is characterised in that (b2) polyalcohol is selected from polyether polyols
One or more in alcohol, PEPA and polycarbonate polyol;(d2) polyalcohol is selected from PPG and gathers
One or more in ester polyol;It is preferred that, described PPG selected from polyethylene glycol, PTMG, four
One or more in hydrogen furans-ethylene oxide copolyether glycol and poly glycol monomethyl ether;Described PEPA is selected from
It is polyethylene glycol adipate, polyadipate hexylene glycol ester, poly adipate succinic acid ester, poly terephthalic acid hexylene glycol ester, poly- right
One or more in benzene dicarboxylic acid butanediol ester and PTT.
5. the resin according to any one of claim 1-4, it is characterised in that poly- (methyl) acrylate is (methyl)
Acrylate, (methyl) acrylate containing NCO reactive groups and the optional small-molecule substance containing carbon-carbon double bond
Polymerizate;
The ester that described (methyl) acrylate is formed selected from (methyl) acrylic acid with the C1-C10 alcohol of saturation, preferably (methyl) third
E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) acrylic acid
Isobutyl ester, (methyl) n-octyl, (methyl) 2-EHA, 1,2- ethylene glycol two (methyl) acrylate,
1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, trimethylolpropane tris (methyl) third
One or more in olefin(e) acid ester and pentaerythrite four (methyl) acrylate, more preferably (methyl) methyl acrylate, (methyl)
One or more in ethyl acrylate, (methyl) n-propyl and (methyl) n-butyl acrylate;
Described (methyl) acrylate containing NCO reactive groups contain at least one can with NCO reaction active group and
At least one (methyl) is acrylate-based;It is preferred that (methyl) hydroxy-ethyl acrylate, hydroxypropyl acrylate, tertiary carbonic acid glycidyl ester
Acrylate, (methyl) acrylic acid 1,3 butylene glycol ester, (methyl) acrylic acid 1,6-HD ester, (methyl) acrylic acid new penta 2
Alcohol ester, bisphenol-A two (methyl) glycidyl acrylate, ethylene-oxide-modified bisphenol-A two (methyl) glycidyl
Ester, trimethylolethane two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl)
Acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five
One or more in (methyl) acrylate and hydroxyl polyester acrylate oligomers;More preferably (methyl) acrylic acid hydroxyl second
Ester, hydroxypropyl acrylate, tertiary carbonic acid glycidyl ester acrylate, pentaerythritol triacrylate, trimethylolpropane dipropyl
One or more in olefin(e) acid ester and Dipentaerythritol Pentaacrylate;
The described small-molecule substance containing carbon-carbon double bond is in ethene, propylene, isobutene, 1,3- butadiene and 1- octenes
One or more.
6. resin according to claim 5, it is characterised in that the small-molecule substance of the carbon-carbon double bond, (methyl) propylene
The mol ratio of acid esters and (methyl) acrylate containing NCO reactive groups is 0~60:50~100:1~50, preferably 0~
40:60~90:1~30.
7. the resin according to any one of claim 1-6, it is characterised in that component (c) silane coupler is selected from end
Base is one or more in the silane coupler of sulfydryl, primary amino radical, secondary amino group or epoxy radicals;It preferably is selected from γ-mercapto propyl group front three
Epoxide alkane, gamma-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-aminopropyl front three
TMOS, gamma-aminopropyl-triethoxy-silane, anilinomethyl trimethoxy silane, anilinomethyl triethoxysilane, N- first
Base γ-aminopropyltrimethoxysilane, N- (normal-butyl)-γ-aminopropyltrimethoxysilane and N- (cyclohexyl)-γ-ammonia third
One or more in base trimethoxy silane.
8. a kind of method for preparing resin described in any one of claim 1-7, comprises the following steps:Proportionally,
(1) component (b) and the reaction of (a) polyisocyanates are prepared into performed polymer;
(2) step (1) gained performed polymer reacts with (c) silane coupler, obtains part by silane epoxide terminated prepolymer;
(3) step (2) gained part is reacted by silane epoxide terminated prepolymer and component (d), and the silane-modified poly- ammonia is obtained
Ester resin.
9. method according to claim 8, it is characterised in that in the step (2) NCO group contained in performed polymer with
C the mol ratio of the NCO reactive groups contained by () silane coupler is 1:0.1~0.8, preferably 1:0.3~0.7.
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