CN106589286A - Silane modified polyurethane resin and preparation method thereof - Google Patents

Abstract

The invention provides a silane-modified polyurethane resin and a preparation method thereof. The resin is obtained by reacting the following raw materials: (a) polyisocyanate; (b) component containing: (b1) poly(meth)acrylate containing NCO reactive groups, and/or, (b2) polyol (c) silane coupling agent; (d) component, containing: (d1) poly(meth)acrylate containing NCO reactive groups, and/or, (d2) polyhydric alcohol; Said raw material is at least Contains one of (b1) and (d1). The poly(meth)acrylate structure is introduced into the branch chain and/or main chain of the silane-modified polyurethane resin, and its resistance to hydrocarbon medium and weather resistance are greatly improved; and the water resistance and heat resistance of polyurethane are introduced to improve Siloxyl. The invention solves the problems of poor resin mechanical strength and poor resistance to hydrocarbon medium.

Description

A kind of silane modified polyurethane resin and preparation method thereof

technical field

The invention relates to a silane-modified polyurethane resin, in particular to a silane-modified polyurethane resin containing a poly(meth)acrylate structure.

Background technique

Polyurethane has the characteristics of high bonding strength, wear resistance, high mechanical strength and good vibration absorption performance, and is widely used in the fields of adhesives, sealants and elastomers. However, due to the existence of free isocyanate, as well as weak heat resistance and water resistance, the application of polyurethane systems in more fields is limited. Based on the above problems, a silane-modified polyurethane system was developed.

Silane-modified polyurethane (SPUR) is the reaction of the terminal isocyanate group of the polyurethane prepolymer into a siloxyl group, and the main chain is a polyurethane segment. The water resistance and heat resistance of silane-terminated polyurethane are improved by introducing weak polarity and high bond energy organosilicon segment. Silane-terminated polyurethane can be used as one-component silane-terminated polyurethane sealant and adhesive.

CN103910847A discloses a method for preparing a silane-modified polyurethane oligomer. The polyurethane sealant thus prepared is limited by the process, so polyether or polyester with lower functionality is selected as the raw material. This will obviously sacrifice the mechanical strength of polyurethane, and the introduction of silicone segments still cannot effectively improve the resistance of polyurethane to the damage of materials by hydrocarbon media.

CN1865313A provides a kind of resin preparation method that hydroxy acrylate exists in silane-modified polyurethane in a small amount in block form, and its silane coupling agent is dibasic alcohol, exists in resin polymer as chain extender, solves the problem to a certain extent Solved the problems of heat resistance and water resistance of urethane acrylate resin, but the operation process is relatively complicated, and the raw materials are relatively limited, which increases the difficulty of use. The system is still an NCO group-terminated polymer, which increases the difficulty of resin preservation, and the unavoidable existence of free isocyanate limits its application in the field of low biological toxicity.

CN101429407A provides a method for improving water resistance and weather resistance of water-based polyurethane by blending silicone-modified water-based polyurethane and polyacrylate. Relying on physical entanglement to solve the performance defects of water-based polyurethane is simple and easy to use, but the improvement effect is general, and the blending process requires the presence of solvents, which conflicts with the environmental protection performance of water-based polyurethane.

The technical solutions of the above patents mainly include two methods: introducing a small amount of modifying components into the main structure, or using physical blending to hybridize materials. Neither of these two methods can essentially improve the performance of the material's resistance to hydrocarbon media.

Contents of the invention

The object of the present invention is to provide a kind of silane-modified polyurethane resin, introduce poly(meth)acrylate structure in polyurethane main chain and/or side chain structure, and introduce the siloxyl group that improves polyurethane water resistance and heat resistance, Solve the problems of poor mechanical strength of resin and poor resistance to hydrocarbon medium.

In order to achieve the above technical purpose, the present invention adopts the following technical solutions:

A kind of silane-modified polyurethane resin, described resin comprises following raw material reaction and obtains: based on the weight of resin,

(a) polyisocyanate, the consumption is 1～40wt%, preferably 5～30wt%;

(b) A component comprising:

(b1) The number of NCO reactive groups per molecule is 1 to 4, preferably 2 to 3, and the number average molecular weight is 100 to 5000g/mol poly(meth)acrylate, the dosage is 0 to 60wt %, preferably 10-50wt%,

and / or,

(b2) a polyhydric alcohol with a number average molecular weight of 60-20000 g/mol, in an amount of 10-60 wt%, preferably 15-50 wt%;

And the content sum of (b1) and (b2) is 10-70wt%, preferably 15-65wt%;

(c) silane coupling agent, the consumption is 0.02～40wt%, preferably 1～30wt%;

(d) component comprising:

(d1) The number of NCO reactive groups per molecule is 2 to 20, preferably 4 to 10, and the number average molecular weight is 3000 to 200000g/mol poly(meth)acrylate, the dosage is 0 to 80wt %, preferably 20～60wt%,

and / or,

(d2) a polyol with a functionality of 3-10 and a number-average molecular weight of 500-30000 g/mol, in an amount of 10-90 wt%, preferably 30-70 wt%;

And the content sum of (d1) and (d2) is 15-80wt%, preferably 25-65wt%;

The raw material contains at least one of (b1) and (d1).

When only (b2) is used in the component (b) of the present invention and (b1) is not used, the component (d) must use (d1), but (d2) may or may not be used.

The amount of raw materials (a) and (b) used in the present invention needs to meet: the molar ratio of the NCO group contained in (a) to the NCO reactive group contained in (b) is 1.5-8:1 , preferably 2 to 5:1.

The molar ratio of the NCO reactive groups in (b), (c) and (d) in the present invention to the NCO groups in (a) is 0.7-1.5, preferably 0.9-1.2.

The (a) polyisocyanate of the present invention is selected from one or more of aliphatic, alicyclic, aromatic and araliphatic polyisocyanates and derivatives thereof with NCO functionality ≥ 2; Iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acyl Polyisocyanate derivatives of one or more of urea and carbodiimide.

Suitable examples of (a) polyisocyanate in the present invention are: 1,4-butanediisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- Trimethyl-1,6-hexanediisocyanate, 2,4,4-trimethyl-1,6-hexanediisocyanate, dicyclohexylmethane diisocyanate (H ₁₂ MDI) and/or its isomers , isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-benzene diisocyanate, 2,4-toluene diisocyanate (TDI) and/or 2, 6-Toluene diisocyanate (TDI), 1,3-bis(2-isocyanatopropan-2-yl)benzene (TMXDI) and 1,4-bis(2-isocyanatopropan-2-yl) Benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI), 2,4-tolylylene diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethane-4,4',4"-triisocyanate; the polyisocyanate can also be a polyisocyanate based on the above examples with more than two -NCO groups Derivatives having uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures.

Preferably, the polyisocyanate is selected from one or more of aliphatic, cycloaliphatic, aromatic and araliphatic diisocyanates, preferably 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthyl diisocyanate, and polyisocyanates in which the aforementioned polyisocyanates are modified by urethane groups.

The functionality of the polyol in component (b2) of the present invention is 2～3, can be polyether, polyester, polycarbonate polyol etc., number average molecular weight 60～20000g/mol, preferred 200～10000g/mol mol, even small molecule polyols with a molecular weight below 200g/mol.

The polycarbonate polyol in component (b2) of the present invention can be synthesized by phosgene method, carbon dioxide regulated copolymerization method, ring-opening polymerization method of cyclic carbonate or transesterification method.

The polycarbonate polyol described in the present invention is preferably synthesized into polycarbonate polyol through transesterification reaction of diol and carbonate.

In the process of synthesizing polycarbonate polyols by the transesterification method of the present invention, the dihydric alcohols include but not limited to 1,2-ethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1, One or more of 6-hexanediol; preferably 1,4-butanediol and/or 1,5-pentanediol. The carbonates include, but are not limited to, dimethyl carbonate and diethyl carbonate; dimethyl carbonate is preferred.

The small molecule polyols described in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2 ,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, decanediol and dodecanediol, glycerin, trimethylolpropane, etc. one or more of.

The polyol of component (d2) in the present invention has a functionality of 3-10, preferably 3-6, and the number average molecular weight of the polyol is 500-30000, preferably 4000-20000. Component (d2) may be polyether, polyester polyol or the like.

The polyether polyol in (b2) and (d2) of the present invention is a polyether polyol prepared by reacting an initiator with an epoxy compound containing 2 to 6 carbon atoms. The initiator is one or more of small molecule polyols, small molecule polyamines and small molecule alcoholamines; including but not limited to water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, One or more of xylitol, sorbitol, bisphenol A, ethylenediamine, triethylenediamine and toluenediamine; preferably one or more of water, propylene glycol and glycerin. The epoxy compound is preferably one or more of ethylene oxide, propylene oxide and tetrahydrofuran (THF).

Preferably, the polyether polyol of the present invention is one or more of polyethylene glycol, polytetrahydrofuran ether glycol, tetrahydrofuran-ethylene oxide copolyether glycol, and polyethylene glycol monomethyl ether.

The polyester polyols in (b2) and (d2) of the present invention can be prepared by esterification or transesterification of dihydric alcohols with dicarboxylic acids, acid anhydrides or dicarboxylic acid esters. The dihydric alcohol is selected from one or more of aliphatic dihydric alcohols and aromatic dihydric alcohols, preferably with 2 to 12 carbon atoms; including but not limited to ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3- Propylene glycol (neopentyl glycol), 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2, One or more of 4-trimethyl-1,3-pentanediol, decanediol and dodecanediol, more preferably ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. Described dibasic carboxylic acid, acid anhydride or dibasic carboxylic acid ester is one or more in aliphatic, alicyclic and aromatic dibasic carboxylic acid, acid anhydride or dibasic carboxylic acid ester, and preferred number of carbon atoms is 4 to 15; including but not limited to phthalic acid, phthalic anhydride, dimethyl phthalate, dimethyl terephthalate, succinic acid, glutaric acid, adipic acid, pimelic acid, One of suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, phthalic anhydride, and tetrahydrophthalic anhydride or more; more preferably one or more of phthalic acid, phthalic anhydride, dimethyl phthalate, dimethyl terephthalate, succinic acid, glutaric acid, adipic acid.

Examples of polyester polyols described in the present invention include, but are not limited to, polyethylene adipate, polyhexamethylene adipate, polybutylene adipate, polyethylene terephthalate ester, polybutylene terephthalate, polytrimethylene terephthalate, etc.

The poly(meth)acrylate of the present invention can be the copolymer containing the small molecular substance of carbon-carbon double bond and (meth)acrylic acid ester, and in order to obtain the poly(meth)acrylic acid containing NCO reactive group Esters, which should also contain at least one monomer of (meth)acrylate containing NCO reactive groups such as (meth)hydroxyethyl acrylate, methacrylic acid, acrylic acid, acrylamide, etc., using ordinary free radical copolymerization or The atom transfer radical polymerization (ATRP) method published by K.Matyjaszewski in J.Am.Chem.SOC.1995,117,5614-5615 and the chain segment transfer freedom as stated in Macromolecules1998,31,5559-5562 by G.Moad et al. Polymers are obtained by means of radical polymerization (RAFT).

Examples of small molecular substances containing carbon-carbon double bonds in the present invention include olefins containing carbon-carbon double bonds such as ethylene, propylene, isobutylene, 1,3-butadiene, and 1-octene.

The (meth)acrylic acid ester described in the present invention includes (meth)acrylic acid ester of saturated alcohol, preferably the ester formed by (meth)acrylic acid and saturated C1-C10 alcohol. Examples of the (meth)acrylate include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate base) isobutyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; preferably (meth) One or more of methyl acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and n-butyl (meth)acrylate.

The (meth)acrylate containing NCO reactive groups in the present invention contains at least one reactive group capable of reacting with NCO and at least one (meth)acrylate group.

Preferably, the (meth)acrylic esters containing NCO reactive groups in the present invention are selected from hydroxyethyl acrylate (abbreviated as HEA), hydroxyethyl methacrylate (abbreviated as HEMA), hydroxypropyl acrylate (abbreviated as HPA), glycidyl acrylate, 1,3-butanediol acrylate, 1,3-butanediol methacrylate, 1,6-hexanediol acrylate, 1,6 methacrylate - Hexylene glycol ester, neopentyl glycol acrylate, neopentyl glycol methacrylate, bisphenol A glycidyl diacrylate, bisphenol A diglycidyl methacrylate, ethylene oxide modified bis Phenol A glycidyl diacrylate, ethylene oxide modified bisphenol A glycidyl dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, trihydroxy Methylpropane Diacrylate, Trimethylolpropane Dimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Dipentaerythritol Triacrylate, Dipentaerythritol Trimethacrylate, Dipentaerythritol Tetraacrylate, One or more of dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and hydroxyl-containing polyester acrylate oligomer.

More preferably, the (meth)acrylic acid ester containing NCO reactive group in the present invention is selected from hydroxyethyl acrylate (abbreviated as HEA), hydroxyethyl methacrylate (abbreviated as HEMA), hydroxypropyl acrylate ( One or more of tertiary carbonic acid glycidyl acrylate, pentaerythritol triacrylate (abbreviated as PETA), trimethylolpropane diacrylate and dipentaerythritol pentaacrylate.

In the raw material of the poly(meth)acrylate described in the present invention, the molar ratio of the small molecular substance of the carbon-carbon double bond, the (meth)acrylate and the (meth)acrylate containing the NCO reactive group is 0～ 60: 50-100: 1-50, preferably 0-40: 60-90: 1-30.

The component (c) silane coupling agent described in the present invention includes one or more of silane coupling agents whose end groups are mercapto, primary amino, secondary amino or epoxy groups.

Examples of the mercapto-terminated silane coupling agent in the present invention include but not limited to γ-mercaptopropyltrimethoxyalane, γ-mercaptopropyltriethoxysilane and the like.

Examples of silane coupling agents containing terminal primary or secondary amino groups in the present invention include, but are not limited to, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Dimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, N-β(ammonia Ethyl)-γ-aminopropyltrimethoxysilane, anilinomethyltrimethoxysilane, anilinomethyltriethoxysilane, N-methylγ-aminopropyltrimethoxysilane, N-(n-butyl base)-γ-aminopropyltrimethoxysilane, N-(cyclohexyl)-γ-aminopropyltrimethoxysilane, etc.

The silane coupling agent containing epoxy group in the present invention includes but not limited to γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyl Triethoxysilane, γ-(2,3-Glycidoxy)propylmethyldimethoxysilane or γ-(2,3-Glycidoxy)propylmethyldiethoxysilane Wait.

The silane coupling agent of the present invention is preferably selected from γ-mercaptopropyl trimethoxy alkane, γ-mercaptopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, anilinomethyltrimethoxysilane, anilinomethyltriethoxysilane, N-methylγ-aminopropyltrimethoxy One or more of N-(n-butyl)-γ-aminopropyltrimethoxysilane and N-(cyclohexyl)-γ-aminopropyltrimethoxysilane.

The present invention also provides a method for preparing the silane-modified polyurethane resin, comprising the following steps:

Following the ratio,

(1) react component (b) with (a) polyisocyanate to prepare prepolymer;

(2) The prepolymer obtained in step (1) is reacted with (c) a silane coupling agent to obtain a part of the prepolymer terminated by siloxy groups;

(3) The part obtained in step (2) reacts the silaneoxy-terminated prepolymer with component (d) to prepare the silane-modified polyurethane resin.

The molar ratio of the NCO group contained in the prepolymer in step (2) of the present invention to the NCO reactive group contained in (c) silane coupling agent is 1:0.1～0.8, preferably 1:0.3～ 0.7.

A catalyst for catalyzing the polyurethane reaction and optionally a solvent may optionally be used in the process of the present invention. Solvents, if used, are removed after the final reaction is complete using methods known in the art.

The catalyst in the present invention includes one or more of tertiary amine catalysts and organometallic catalysts.

The tertiary amine catalysts described in the present invention include pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, N-methylimidazole, 1,2-dimethylimidazole, N,N-dimethyl Cyclohexylamine, N-methyldicyclohexylamine, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, triethylamine, tributylamine, 1,4 -Dimethylpiperazine, N,N-dimethylbenzylamine, N,N-dimethyl(hexadecyl)amine, bis(dimethylaminoethyl)ether, N,N,N', N'-Tetramethylethylenediamine, N,N,N',N'-Tetramethylpropylenediamine, N,N,N',N'-Tetramethylbutylenediamine, N,N,N' ,N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethyldiaminodicyclohexylmethane, triethanolamine, triisopropanolamine, tris(dimethylaminopropyl)amine, One of N-methyldiethanolamine, N-ethyldiethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylpropylenediamine, trimethylhydroxyethylethylenediamine and dimethylethanolamine or more; preferably triethylenediamine, bis(dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, N-methyldicyclohexylamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, tris(dimethylaminopropyl )amine, N,N-dimethylbenzylamine, N,N-dimethyl(hexadecyl)amine, dimethylethanolamine, dimethylaminoethoxyethanol, trimethylhydroxyethylpropylenediamine , one or more of trimethylhydroxyethylethylenediamine, N-methylmorpholine, N-ethylmorpholine and triethylamine.

Organometallic catalysts of the present invention, such as organic potassium compounds, organic tin compounds, such as tin (II) salts of organic carboxylic acids, such as tin (II) diacetate, tin (II) dioctoate, di(ethyl) Tin(II) hexanoate and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and diacetate diacetate Octyl tin. Other compounds which are very suitable are dialkyltin(IV) mercapto compounds, such as dilauryltin(IV) dithiolate, and the general formula R ₂ Sn(SR'-O-CO-R") ₂ or R ₂ Compounds of Sn(SR'-CO-OR") ₂ , where R is an alkyl group having at least 8 carbon atoms, R' is an alkyl group having at least 2 carbon atoms, and R" is an alkyl group having at least 4 carbon atoms of alkyl.

Examples of such catalysts as disclosed in DD-A-218668 are: dioctyltin-bis(2-ethylhexanoic acid thioethylene glycol ester), dioctyltin-bis(lauric acid thioethylene glycol ester) ), dioctyltin-bis(2-ethylhexyl thiolate acetate), dioctyltin-bis(hexyl thiolate acetate), and dioctyltin-bis(lauryl thiolate acetate). Other catalysts which are very suitable are the general formula (R ₃ Sn) ₂ O, R ₂ SnS, (R ₃ Sn) ₂ S, R ₂ Sn, (SR') ₂ or RSn(SR') as disclosed in DD-A-255535 ') ₃ organotin compounds having tin-oxygen or tin-sulfur bonds, where R and R' are 4 to 8 carbon atoms (in the case of R) and 4 to 12 carbon atoms (in the case of R' case), R' can also be -R"COOR" or -R"COOR, wherein R" is an alkyl group having 1 to 6 carbon atoms, and R is an alkylene group having 4 to 12 carbon atoms. Examples that may be mentioned are: bis(tributyltin) oxide, dibutyltin sulfide, dioctyltin sulfide, bis(tributyltin) sulfide, dibutyltin-(2-ethylhexylthioglycolate), Dioctyltin-bis(2-ethylhexylthioglycolate), Octyltin-tris(2-ethylhexylthioglycolate), Dioctyltin-bis(2-ethylhexylthioglycolate) alcohol esters) and dibutyltin-di(thioethylene glycol laurate).

Examples of suitable organic potassium compounds include, but are not limited to, potassium isooctanoate, potassium acetate, potassium oleate, and the like.

Examples of suitable organometallic catalysts may also be other organometallic compounds, such as tetrabutyl titanate, zinc isooctanoate, and the like.

The organometallic compounds can be used as catalysts alone or in the form of catalyst compositions.

The organometallic catalyst described in the present invention preferably includes one or more of potassium isooctanoate, potassium acetate, dibutyltin dilaurate, tetrabutyl titanate, zinc isooctanoate, stannous octoate and potassium oleate.

All solvents customarily used in polyurethane chemistry can be used as the solvents mentioned above. Especially esters, ketones, halogenated hydrocarbon compounds, paraffins, alkenes and aromatic compounds. Examples of such solvents are methylene chloride, trichloroethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate, cyclohexane, Cyclohexenone, Dichlorobenzene, Diethyl Ketone, Diisobutyl Ketone, Dioxane, Ethyl Acetate, Ethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Monoethyl Acetate , 2-ethylhexyl acetate, ethylene glycol diacetate, heptane, hexane, isobutyl acetate, isooctane, isopropyl acetate, acetone, methyl ethyl ketone, tetrahydrofuran or tetrachloroethylene, etc. one or more.

In a specific application, considering that the viscosity of the silane-modified polyurethane resin is too high, the part of the silaneoxy-terminated prepolymer obtained in steps (1) to (2) can be used as the A component, and the (d) component can be used as the For component B, store components A and B separately and use them in two-component form. Optional additives known in the art can be added to the A component and the B component. Said auxiliary agent includes but not limited to filler, plasticizer etc., the example of said filler includes asbestos powder, silica gel powder, phenolic resin, porcelain powder, titanium dioxide, alumina powder, graphite powder, kaolin powder, aluminum disulfide powder, Carbon black, white carbon black, organic bentonite, polyamide, active calcium, talcum powder, etc.; Examples of the plasticizer include diisooctyl phthalate, dioctyl phthalate, di Butyl ester, benzyl phthalate, diisononyl phthalate, diisodecyl phthalate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate , acetyl tri-n-butyl citrate, 1,2-diisononyl cyclohexanedioate, etc.; the catalyst can also be added to A or B component as a curing accelerator.

The silane-modified polyurethane resin of the present invention is resistant to hydrocarbon medium, exceeds the requirements of GB/T 539-2008, has a weight gain rate of <30%, and a thickness increase rate of 0-20%.

The hydrocarbon medium in the present invention includes petroleum deep-processing products, such as gasoline, kerosene, diesel oil, lubricating oil, asphalt, various solvent oils, and the like.

The silane-modified polyurethane resin of the present invention utilizes the self-advantages of a variety of polymer materials to organically combine to realize functional diversity and complexity, especially to introduce a certain proportion on the main chain and/or side chain The poly(meth)acrylate improves the hydrocarbon medium resistance of the material; in addition, when the main chain and side chain of the resin material are introduced into poly(meth)acrylate, its hydrocarbon medium resistance and weather resistance are improved. It is greatly improved; the raw materials used in the present invention are easy to obtain, the synthesis process is simple, and uncontrollable reactions are not easy to occur; and the material properties can be widely adjusted through simple adjustment of proportion or change of feeding sequence.

detailed description

Refer to GB3912-1983 for thickness increase rate and weight gain rate, and GB/T 528-2009 for mechanical performance test.

Embodiment one

The preparation of silane modified polyurethane prepolymer: 400g number average molecular weight is 2000 Add 2056 (Wanhua Chemical) and 133.2g IPDI into a 5L three-necked flask, preheat to 50-60°C while stirring, add 0.1g stannous octoate catalyst and react at 60°C for 2 hours, then add 117.6g γ-mercaptopropane Trimethoxysilane continued to react for 1 h to obtain a silane-modified polyurethane prepolymer.

After that, the polymethacrylate (functionality=5.4; number average molecular weight=9300g/mol; glass transition temperature=-5°C; methyl methacrylate/styrene/butyl acrylate/methyl methacrylate) added to the system The molar ratio of hydroxyethyl acrylate = 1:0.3:2:1.3 (prepared by free radical polymerization) 344.4g and N,N-dimethylformamide 2L mixed solution, reacted for 2 hours, and heated in vacuum to remove the solvent.

The above-mentioned silane-modified polyurethane was cast into a film with a thickness of 2 mm, and cured for 21 days at a temperature of 23° C. and a humidity of 50%, to obtain a homogeneous film without bubbles. Surface dry time is 3 hours, hard work time is 13 hours. The tensile strength of the film is 15MPa, and the elongation at break is 411%; after soaking in American standard test oil (IRM903) for 72h, the thickening rate=5%, the weight gain=7%, the tensile strength is 13MPa, and the elongation at break 452%.

Embodiment two

Preparation of silane-modified polyurethane prepolymer: 200g polycarbonate polyol (Asahi Kasei; T5651, number average molecular weight is 1000g/mol, functionality=2), 200g polymethacrylate (functionality=2.1; number average Molecular weight=2000, glass transition temperature=-23°C; methyl methacrylate/isooctyl acrylate/hydroxyethyl methacrylate molar ratio=1:2.7:1.2 prepared by free radical polymerization) and 116.7g TDI was added to In a 3L three-necked flask, preheat 50-60°C while stirring, add 0.1g of stannous octoate catalyst and react at 60°C for 2h, then add 158g of anilinomethyltriethoxysilane and continue the reaction for 1h to obtain silane-modified Polyurethane prepolymers.

After that, 400 g of polyether polyol (Gaoqiao Petrochemical; GEP-828, number average molecular weight 6000, functionality=3) and 200 mL of acetone were added to the system, and the reaction was continued for 5 h.

The above-mentioned silane-modified polyurethane was cast into a film with a thickness of 2 mm, and cured for 7 days at a temperature of 23° C. and a humidity of 50%, to obtain a homogeneous film without bubbles. The surface dry time is 5h, and the hard dry time is 20h. The tensile strength of the film is 5.2MPa, and the elongation at break is 370%; after soaking in American standard test oil (IRM903) for 72h, the thickening rate=4%, the weight gain=5%, the tensile strength is 2.9MPa, and the elongation at break The length is 390%.

Embodiment three

Preparation of silane-modified polyurethane prepolymer: 400g polymethacrylate (functionality=2.1; number average molecular weight=4000g/mol, glass transition temperature=-8°C; methyl methacrylate/isooctyl acrylate /butyl acrylate/hydroxyethyl methacrylate molar ratio=1:1.3:1.8:1 prepared by free radical polymerization) and 150gMDI into a 5L three-necked flask, preheated to 50-60°C while stirring, added 0.1 g of tin neodecanoate catalyst was reacted at 60°C for 2 h, and then 165 g of cyclohexylaminomethyltriethoxysilane was added to continue the reaction for 1 h to obtain a silane-modified polyurethane prepolymer.

Then add 1600g polymethacrylate (functionality=5; number average molecular weight=20000g/mol; glass transition temperature=-17°C; ethyl methacrylate/butyl acrylate/isooctyl acrylate/ The molar ratio of hydroxyethyl methacrylate = 1:1.5:1.3:1.3 (prepared by atom transfer radical polymerization) and N,N-dimethylformamide 2L solution, reacted for 2 hours, and heated in vacuum to remove the solvent.

The above-mentioned silane-modified polyurethane was cast into a film with a thickness of 2 mm, and cured for 7 days at a temperature of 25° C. and a humidity of 50%, to obtain a homogeneous film without bubbles. The surface dry time is 5h, and the hard dry time is 20h. The tensile strength of the film is 4.9MPa, and the elongation at break is 479%; after soaking in American standard test oil (IRM903) for 72h, the thickening rate=3%, the weight gain=3%, the tensile strength is 4.8MPa, and the elongation at break is 479%. The length is 512%.

Embodiment four

The preparation of silane-modified polyurethane prepolymer: the polyester diol ( PN-110) and 126g of 1,5-naphthalene diisocyanate were added to a 5L three-necked flask, preheated to 50-60°C while stirring, added 0.1g of stannous octoate catalyst and reacted at 60°C for 2h, then added 89.5gγ -Aminopropyltrimethoxysilane continued to react for 1 hour to obtain a silane-modified polyurethane prepolymer.

Then add polymethacrylate (functionality=5.4; number average molecular weight=9300g/mol; glass transition temperature=-6°C; methyl methacrylate/butyl acrylate/hydroxyethyl methacrylate to the system) Molar ratio = 1:2:1.3 (prepared by free radical polymerization) 516.7g and N,N-dimethylformamide 3L mixed solution, reacted for 2h, then heated in vacuum to remove the solvent.

The above-mentioned silane-modified polyurethane was cast into a film with a thickness of 2 mm, and cured for 21 days at a temperature of 23° C. and a humidity of 50%, to obtain a homogeneous film without bubbles. Surface dry time is 3 hours, hard work time is 13 hours. The tensile strength of the film is 25MPa, and the elongation at break is 394%; after soaking in American standard test oil (IRM903) for 72h, the thickening rate=4%, the weight gain=6%, the tensile strength is 23MPa, and the elongation at break 352%.

comparative example

Preparation of silane-modified polyurethane prepolymer: 200g number average molecular weight is 1000 polycarbonate polyols (Asahi Kasei; T5651, number average molecular weight is 1000g/mol, functionality=2) and 150gMDI are added in the 5L three-necked flask , preheated to 50-60°C while stirring, added 0.1g of stannous octoate catalyst and reacted at 60°C for 2h, then added 110g of anilinomethyltriethoxysilane and continued to react for 1h to obtain a silane-modified polyurethane prepolymer .

Then add 650g to the system A mixed solution of 3135 (number-average molecular weight: 5000g/mol, functionality=3) and N,N-dimethylformamide 2L, reacted for 2h, then heated in vacuum to remove the solvent.

The above-mentioned silane-modified polyurethane was cast into a film with a thickness of 2 mm, and cured for 21 days at a temperature of 23° C. and a humidity of 50%, to obtain a homogeneous film without bubbles. Surface dry time is 2.5h, hard dry time is 12h. The tensile strength of the film is 13MPa, and the elongation at break is 611%; after soaking in American standard test oil (IRM903) for 72h, the thickening rate=50%, the weight gain=57%, the tensile strength is 3MPa, and the 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.