CN104292412A - Cellulose base polyurethane prepolymer as well as sealing material using cellulose base polyurethane prepolymer, preparation method and application of cellulose base polyurethane prepolymer - Google Patents
Cellulose base polyurethane prepolymer as well as sealing material using cellulose base polyurethane prepolymer, preparation method and application of cellulose base polyurethane prepolymer Download PDFInfo
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- CN104292412A CN104292412A CN201410533009.9A CN201410533009A CN104292412A CN 104292412 A CN104292412 A CN 104292412A CN 201410533009 A CN201410533009 A CN 201410533009A CN 104292412 A CN104292412 A CN 104292412A
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
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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
- C08G18/08—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
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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
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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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses cellulose base polyurethane prepolymer as well as a sealing material using the cellulose base polyurethane prepolymer, a preparation method and application of the cellulose base polyurethane prepolymer. The cellulose base polyurethane prepolymer comprises a component A, polyether polyol and isocyanate, wherein the component A comprises an ionic liquid, cellulose and polyether polyol; the sealing material comprises the prepolymer and a component B, wherein the component B comprises polyether polyol, packing, a coupling agent, a catalyst, an antioxidant and an ultraviolet absorbent. The technical problems in the prior art that a cellulose base polyurethane material is high in hardness, poor in elasticity and easy to crack and moreover a sealing material is easy to damage as the requirements of modulus and hardness cannot be met at the same time, are solved. The obtained polyurethane sealing material which is low in hardness, high in flexibility, low in modulus and high in strength is free of quick deterioration and damage when subjected to relatively large deformation under extreme natural conditions such as high temperature, strong breeze and earthquake, and is particularly applicable to seam joint of concrete buildings, roads, bridges and plane runways, mounting of glass and filling of electronic devices.
Description
Technical field
The present invention relates to a kind of polyurethane sealing material and preparation method, relate in particular to a kind of cellulose base base polyurethane prepolymer for use as and use its sealing material and preparation method.
Background technology
Sealing material refer to can bear seam displacement to reach airtight, watertight object and the material embedded in object seam, usually have both bonding and sealing two large functions, good physical and mechanical property should be had, rebound resilience is high, compression set is little, seal the advantages such as reliable, easy to process and long service life.
According to different application conditions, sealing material mainly comprises silicone, poly-sulphur class and polyurethanes sealing material three kinds, and wherein silicone sealing material can high temperature resistant and low temperature, radiation hardness, vacuum-resistant, pollution-free, nontoxic, but cohesiveness is relatively poor; Poly-sulphur class sealing material has good cementability to the material such as metal and concrete, can keep good resistance to air loss and water-repellancy, and oil resistant, solvent resistant, weather resistance are better, but its anti-ultraviolet ageing performance is poor under continuous and adjustable, vibration and temperature variation; Polyurethanes sealing material is a kind of emerging organic polymer material, there is good ageing resistance, high and low temperature resistance and fatigue performance, also there is excellent wear resistance, cohesiveness, oil-proofness and resistance to biodeterioration energy, and performance variable range is wide, strong adaptability, good springiness, have excellent Restoration, can be used for dynamic juncture, polyurethanes sealing material is widely used in national economy various fields because of the performance of its above-mentioned brilliance.
Mierocrystalline cellulose is a kind of natural macromolecular material, for promoting the performance of polyurethane material further, in conventional urethane material, add cellulosic research cause and pay close attention to widely, the such as preparation of cellulose base polyurethane material " in the imidazolium ionic liquid " (Guangdong chemical industry, 2010, 5 (37), 52.) a kind of preparation method of cellulose base polyurethane material is disclosed in, first isocyanic ester and polyether glycol react and generate base polyurethane prepolymer for use as by the method, and then base polyurethane prepolymer for use as is joined in the ionic liquid of dissolving cellulos, by ionic liquid removal of solvents after reaction, obtain cellulose base polyurethane material, find after deliberation, the cellulose base polyurethane material that the method obtains has good thermostability, but because Mierocrystalline cellulose easily occurs clustering phenomena in ionic liquid, it is made to be difficult to fully be dissolved in ionic liquid, the cellulose macromolecule of reuniting makes polyurethane molecular internal stress increase, thus make the polyurethane material hardness of generation high, poor flexibility, easy to crack.
Summary of the invention
For this reason, technical problem to be solved by this invention to be in prior art that cellulose base polyurethane material hardness is high, poor flexibility, problem easy to crack, and then proposes a kind of soft, elastomeric sealing material.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of cellulose base base polyurethane prepolymer for use as, comprise component A, 60-80 weight part polyether glycol, 10-25 weight part isocyanic ester, described component A comprises 5-12 weight part ionic liquid, 1-5 part by weight of cellulose and 20-40 weight part polyether glycol.
Described polyether glycol is the trivalent alcohol of mass ratio 2:1-4.5:1 and the mixture of dibasic alcohol formation.
The relative molecular weight of described trivalent alcohol is 4000-6000, and the relative molecular weight of described dibasic alcohol is 2000-4000.
Described dibasic alcohol is one or more in Polyoxyethylene glycol, polyoxypropyleneglycol, polytetrahydrofuran diol, and described trivalent alcohol is one or more in polyoxytrimethylene triol, oxypropylene-oxyethylene copolyether triol, Viscotrol C.
Described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-allyl group-3-Methylimidazole villaumite, 1-butyl-3-Methylimidazole villaumite or 1-vinyl-3-butyl imidazole villaumite.
Described isocyanic ester is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
Further, described cellulose base base polyurethane prepolymer for use as also comprises the promotor of 0.05-0.5 weight part, and described promotor is dibutyl tin laurate or triethylamine.
A kind of sealing material comprising described cellulose base base polyurethane prepolymer for use as, also comprise B component, described B component comprises polyether glycol described in 20-40 weight part, 15-50 parts of filler material by weight, 0.2-1.5 weight part coupling agent, 0.1-0.5 part by weight of catalyst, 0.2-1.5 weight part oxidation inhibitor and 0.1-1 weight part uv-absorbing agent.
Described filler is one or more in silicon-dioxide, calcium carbonate, calcium oxide, flyash, talcum powder, kaolin, carbon black and titanium dioxide.
Described coupling agent is γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane;
Described catalyzer is lead octoate 36, stannous octoate, dibutyl tin laurate, N-ethylmorpholine or N, N-dimethylcyclohexylamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described uv-absorbing agent be 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3-dodecyl-5-methyl) benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole or 2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole.
The mass ratio of described cellulose base base polyurethane prepolymer for use as and described B component is 3:1.
Prepare a method for described sealing material, comprise the steps:
(1) preparation of cellulose base base polyurethane prepolymer for use as
At S1,60-100 DEG C, after desired ion liquid and Mierocrystalline cellulose being mixed, add a certain amount of polyether glycol wherein, and be warming up to 105-120 DEG C, stir 2-3h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2, general more a certain amount of polyether polyols dehydration of alcohols obtain the polyether glycol that dewaters, and sealing saves backup;
S3, under nitrogen protection, isocyanic ester is warming up to 60-70 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in isocyanic ester in 1h, be warming up to 80-100 DEG C, reaction 1-3h, then add the obtained dehydrating mixt of described S1, continue reaction 1-2h, be cooled to 40-60 DEG C, obtain described component A;
(2) preparation of B component
S4, described filler to be dried at 105-115 DEG C, for subsequent use;
S5, at 40-60 DEG C, the described filler after oven dry is added in a certain amount of polyether glycol again, stirring makes described polyether glycol mix with uniform filling, coupling agent is dripped in the mixture obtained, stir, finally add catalyzer, oxidation inhibitor and uv-absorbing agent, Keep agitation 0.5-1h, obtain described B component.
The step adding promotor is also comprised in described step S3.
Described step S2, for a certain amount of polyether glycol is warming up to 110-120 DEG C, under vacuum tightness is 0.097MPa, stirs 2-3h, is then cooled to 60 DEG C, obtains the polyether glycol after dewatering.
Described sealing material is installed in the seam of concrete structure, highway, bridge, airstrip and glass, electron device filling in application.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) cellulose base base polyurethane prepolymer for use as of the present invention, first by ionic liquid, after Mierocrystalline cellulose and polyether glycol mix, obtain component A, adding a part of polyether glycol with during ion liquid dissolving Mierocrystalline cellulose, make Mierocrystalline cellulose under the promotion of polyether glycol, fully be dissolved in ionic liquid, and form the continuous phase solution of Mierocrystalline cellulose-polyether glycol-ionic liquid, further its with isocyanic ester with dewater after polyether glycol be obtained by reacting performed polymer time, Mierocrystalline cellulose can be dispersed in polyurethane molecular uniformly, reduce molecule internal stress, avoid because Mierocrystalline cellulose is assembled that to cause molecule internal stress to increase the material caused partially hard, poor flexibility, problem easy to crack.
(2) cellulose base polyurethane sealing material of the present invention, the chemistry played in polyurethane system due to Mierocrystalline cellulose connects and physical, framework effect, the intensity of polyurethane sealing material is got a promotion, do not need with organic solvent, ionic liquid to be removed, simplify preparation process, avoid environmental pollution; Ionic liquid is stayed in system simultaneously, can be used as excellent plasticising lubrication barrier agent, is isolated by polyurethane molecular, promote the slippage that chain is intersegmental and motion, make polyurethane sealing material have low modulus while high strength.
(3) cellulose base polyurethane sealing material of the present invention has that hardness is low, elasticity is high and the advantage that modulus is low, intensity is high, can not produce rotten and damage sharply when there is moderate finite deformation under the extreme natural condition such as high temperature, high wind, earthquake.After tested, cellulose base polyurethane sealing material hardness (shore A) described in the application is less than 25, tensile modulus is less than 0.3MPa, tensile strength is greater than 1.6MPa, thermal ageing process 168h at 80 DEG C, stretching strength retentivity and elongation at break conservation rate >=80%, after ultraviolet ageing 720h, stretching strength retentivity and elongation at break conservation rate >=90%, after alkaline purification 168h, stretching strength retentivity and elongation at break conservation rate >=80%.
Embodiment
In order to make the object, technical solutions and advantages of the present invention clearly, will be described in further detail embodiments of the present invention below.
Embodiment 1
The present embodiment provides a kind of cellulose base polyurethane sealing material, comprise cellulose base base polyurethane prepolymer for use as and B component, described cellulose base base polyurethane prepolymer for use as comprises component A, the polyether glycol of 70g, 20g tolylene diisocyanate and 0.3g dibutyl tin laurate; Wherein component A comprises the polyether glycol of 8g1-ethyl-3-methylimidazole bromine salt, 3g Mierocrystalline cellulose, 30g;
Described 1-ethyl-3-methylimidazole bromine salt is purchased from the purple chemical reagent work in Shanghai, and purity is 98%.
B component comprises 30g polyether glycol, 32g silicon-dioxide, 0.8g γ-aminopropyl triethoxysilane, 0.3g lead octoate 36,0.8g 2,6 ditertiary butyl p cresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole.
In the present embodiment, the relative molecular weight that described polyether glycol is 3:1 by mass ratio be 5000 polyoxytrimethylene triol and relative molecular weight be that 3000 Polyoxyethylene glycols form.
The preparation method of the cellulose base polyurethane sealing material described in the present embodiment is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 80 DEG C, after 8g1-ethyl-3-methylimidazole bromine salt and 3g Mierocrystalline cellulose being mixed, add the polyether glycol of 30g wherein, and be warming up to 110 DEG C, stir 2.5h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,70g polyether glycol is warming up to 115 DEG C, under vacuum tightness is 0.97MPa, stirs 2.5h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 20g tolylene diisocyanate is warming up to 65 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in described tolylene diisocyanate in 1h, then add 0.3g dibutyl tin laurate, be warming up to 90 DEG C, reaction 2h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1.5h, be cooled to 50 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,32g silicon-dioxide to be dried at 110 DEG C, for subsequent use;
S5, at 50 DEG C, the silicon-dioxide after oven dry is added in 30g polyether glycol, stirring makes described polyether glycol and described silicon-dioxide Homogeneous phase mixing, in the mixture obtained, drip 0.8g γ-aminopropyl triethoxysilane, stir, finally add 0.3g lead octoate 36,0.8g 2,6-ditertbutylparacresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, Keep agitation 50min, obtains described B component.
During use, by described cellulose base base polyurethane prepolymer for use as and described B component in mass ratio 3:1 mix.
Embodiment 2
The present embodiment provides a kind of cellulose base polyurethane sealing material, comprise cellulose base base polyurethane prepolymer for use as and B component, described cellulose base base polyurethane prepolymer for use as comprises component A, 60g polyether glycol, 10g diphenylmethanediisocyanate and 0.05g dibutyl tin laurate; Wherein component A comprises 5g 1-allyl group-3-Methylimidazole villaumite, 1g Mierocrystalline cellulose, 20g polyether glycol;
Described 1-allyl group-3-Methylimidazole villaumite is purchased from the purple chemical reagent work in Shanghai, and purity is 98%.
B component comprises 20g polyether glycol, 8g calcium carbonate, 7g calcium oxide, 0.2g γ-glycidyl ether oxygen propyl trimethoxy silicane, 0.1g stannous octoate, 0.2g 2,6 ditertiary butyl p cresol and 0.1g2-(2-hydroxyl-3-dodecyl-5-methyl) benzotriazole.
In the present embodiment, the relative molecular weight that described polyether glycol is 2:1 by mass ratio be 4000 oxypropylene-oxyethylene copolyether triol and relative molecular weight be that 2000 polyoxypropyleneglycols form.
The preparation method of the cellulose base polyurethane sealing material described in the present embodiment is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 60 DEG C, after 5g1-allyl group-3-Methylimidazole villaumite and 1g Mierocrystalline cellulose being mixed, add 20g polyether glycol wherein, and be warming up to 105 DEG C, stir 2h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,60g polyether glycol is warming up to 110 DEG C, under vacuum tightness is 0.97MPa, stirs 2h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 10g diphenylmethanediisocyanate is warming up to 60 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in described diphenylmethanediisocyanate in 1h, then add 0.05g dibutyl tin laurate, be warming up to 80 DEG C, reaction 1h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1h, be cooled to 40 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,8g calcium carbonate and 7g calcium oxide to be dried at 105 DEG C, for subsequent use;
S5, at 40 DEG C, the calcium carbonate after oven dry and calcium oxide is added in 20g polyether glycol, stirring makes described polyether glycol and described calcium carbonate, calcium oxide Homogeneous phase mixing, 0.2g γ-glycidyl ether oxygen propyl trimethoxy silicane is dripped in the mixture obtained, stir, finally add 0.1g stannous octoate, 0.2g 2,6 ditertiary butyl p cresol and 0.1g 2-(2-hydroxyl-3-dodecyl-5-methyl) benzotriazole, Keep agitation 30min, obtains described B component.
During use, by described cellulose base base polyurethane prepolymer for use as and described B component in mass ratio 3:1 mix.
Embodiment 3
The present embodiment provides a kind of cellulose base polyurethane sealing material, comprises cellulose base base polyurethane prepolymer for use as and B component, and described cellulose base base polyurethane prepolymer for use as comprises component A, 80g polyether glycol, 25g isophorone diisocyanate and 0.5g triethylamine; Wherein component A comprises 12g1-butyl-3-Methylimidazole villaumite, 5g Mierocrystalline cellulose, 40g polyether glycol;
Described 1-butyl-3-Methylimidazole villaumite is purchased from the purple chemical reagent work in Shanghai, and purity is 98%.
B component comprises 40g polyether glycol, 20g flyash, 20g talcum powder, 10g kaolin, 1.5g γ-methacryloxypropyl trimethoxy silane, 0.5g dibutyl tin laurate, 1.5g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole.
In the present embodiment, the relative molecular weight that described polyether glycol is 4.5:1 by mass ratio be 6000 Viscotrol C and relative molecular weight be 4000 polytetrahydrofuran diol form.
The preparation method of the cellulose base polyurethane sealing material described in the present embodiment is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 100 DEG C, after 12g1-butyl-3-Methylimidazole villaumite and 5g Mierocrystalline cellulose being mixed, add 40g polyether glycol wherein, and be warming up to 120 DEG C, stir 3h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,80g polyether glycol is warming up to 120 DEG C, under vacuum tightness is 0.97MPa, stirs 3h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 25g isophorone diisocyanate is warming up to 70 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in isocyanic ester in 1h, then add 0.5g triethylamine, be warming up to 100 DEG C, reaction 3h, add the dehydrating mixt that described S1 is obtained again, continue reaction 2h, be cooled to 60 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,20g flyash, 20g talcum powder, 10g kaolin to be dried at 115 DEG C, for subsequent use;
S5, at 60 DEG C, the flyash after oven dry is added in 40g polyether glycol, talcum powder and kaolin, stirring makes described polyether glycol and described flyash, talcum powder and kaolin Homogeneous phase mixing, 1.5g γ-methacryloxypropyl trimethoxy silane is dripped in the mixture obtained, stir, finally add 0.5g dibutyl tin laurate, 1.5g tetra-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole, Keep agitation 1h, obtain described B component.
During use, by described cellulose base base polyurethane prepolymer for use as and described B component in mass ratio 3:1 mix.
Embodiment 4
The present embodiment provides a kind of cellulose base polyurethane sealing material, comprises cellulose base base polyurethane prepolymer for use as and B component, and described cellulose base base polyurethane prepolymer for use as comprises component A, 40g polyether glycol, 25g hexamethylene diisocyanate and 0.5g triethylamine; Wherein component A comprises 5g 1-vinyl-3-butyl imidazole villaumite, 5g Mierocrystalline cellulose, 20g polyether glycol;
Described 1-butyl-3-Methylimidazole villaumite is purchased from the purple chemical reagent work in Shanghai, and purity is 98%.
B component comprises 20g polyether glycol, 15g carbon black, 15g talcum powder, 20g titanium dioxide, 0.2g γ-methacryloxypropyl trimethoxy silane, 0.5gN-ethyl morpholine, 0.2g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g 2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole.
In the present embodiment, the relative molecular weight that described polyether glycol is 2:1 by mass ratio be 4000 trivalent alcohol and relative molecular weight be 2000 dibasic alcohol form; Trivalent alcohol comprises oxypropylene-oxyethylene copolyether triol and polyoxytrimethylene triol, and the mass percent that described oxypropylene-oxyethylene copolyether triol accounts for described trivalent alcohol is 50wt%; Dibasic alcohol comprises Polyoxyethylene glycol and polyoxypropyleneglycol, and the mass percent that wherein said Polyoxyethylene glycol accounts for described dibasic alcohol is 50wt%.
The preparation method of the cellulose base polyurethane sealing material described in the present embodiment is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 100 DEG C, after 5g1-vinyl-3-butyl imidazole villaumite and 5g Mierocrystalline cellulose being mixed, add 20g polyether glycol wherein, and be warming up to 120 DEG C, stir 2h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,40g polyether glycol is warming up to 120 DEG C, under vacuum tightness is 0.97MPa, stirs 2h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 25g hexamethylene diisocyanate is warming up to 70 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in isocyanic ester in 1h, then add 0.5g triethylamine, be warming up to 100 DEG C, reaction 1h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1h, be cooled to 60 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,5g carbon black, 5g talcum powder, 5g titanium dioxide to be dried at 105 DEG C, for subsequent use;
S5, at 60 DEG C, the carbon black after oven dry is added in 20g polyether glycol, talcum powder and titanium dioxide, stirring makes described polyether glycol and described carbon black, talcum powder and titanium dioxide Homogeneous phase mixing, 0.2g γ-methacryloxypropyl trimethoxy silane is dripped in the mixture obtained, stir, finally add 0.5gN-ethyl morpholine, 0.2g tetra-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole, Keep agitation 30min, obtain described B component.
During use, by described cellulose base base polyurethane prepolymer for use as and described B component in mass ratio 3:1 mix.
Embodiment 5
The present embodiment provides a kind of cellulose base polyurethane sealing material, comprise cellulose base base polyurethane prepolymer for use as and B component, described cellulose base base polyurethane prepolymer for use as comprises component A, 80g polyether glycol, 20g tolylene diisocyanate, 5g hexamethylene diisocyanate and 0.4g dibutyl tin laurate; Wherein component A comprises 10g 1-vinyl-3-butyl imidazole villaumite, 5g Mierocrystalline cellulose, 20g polyether glycol;
Described 1-butyl-3-Methylimidazole villaumite is purchased from the purple chemical reagent work in Shanghai, and purity is 98%.
B component comprises 40g polyether glycol, 15g silicon-dioxide, 15g talcum powder, 0.2g γ-methacryloxypropyl trimethoxy silane, 0.5gN, N-dimethylcyclohexylamine, 0.2g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole.
In the present embodiment, the relative molecular weight that described polyether glycol is 4:1 by mass ratio be 4000 oxypropylene-oxyethylene copolyether triol and relative molecular weight be 2000 polyoxypropyleneglycol form.
The preparation method of the cellulose base polyurethane sealing material described in the present embodiment is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 100 DEG C, after 10g 1-vinyl-3-butyl imidazole villaumite and 5g Mierocrystalline cellulose being mixed, add 20g polyether glycol wherein, and be warming up to 110 DEG C, stir 2h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,80g polyether glycol is warming up to 120 DEG C, under vacuum tightness is 0.97MPa, stirs 1.5h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 20g tolylene diisocyanate, 5g hexamethylene diisocyanate are warming up to 70 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in isocyanic ester in 1h, then add 0.4g dibutyl tin laurate, be warming up to 100 DEG C, reaction 1h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1h, be cooled to 60 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,15g silicon-dioxide, 15g talcum powder to be dried at 105 DEG C, for subsequent use;
S5, at 60 DEG C, the silicon-dioxide after oven dry is added in 40g polyether glycol, talcum powder, stirring makes described polyether glycol and described silicon-dioxide, talcum powder Homogeneous phase mixing, 0.2g γ-methacryloxypropyl trimethoxy silane is dripped in the mixture obtained, stir, finally add 0.5gN, N-dimethylcyclohexylamine, 0.2g tetra-[β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 1g2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole, Keep agitation 30min, obtain described B component.
During use, by described component A and described B component in mass ratio 3:1 mix.
Comparative example 1
This comparative example provides a kind of cellulose base polyurethane sealing material, comprise cellulose base base polyurethane prepolymer for use as and B component, described cellulose base base polyurethane prepolymer for use as comprises 8g 1-ethyl-3-methylimidazole bromine salt, 3g Mierocrystalline cellulose, 100g polyether glycol, 20g tolylene diisocyanate and 0.3g dibutyl tin laurate;
B component comprises 30g polyether glycol, 32g silicon-dioxide, 0.8g γ-aminopropyl triethoxysilane, 0.3g lead octoate 36,0.8g 2,6 ditertiary butyl p cresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole.
In this comparative example, the relative molecular weight that described polyether glycol is 3:1 by mass ratio be 5000 polyoxytrimethylene triol and relative molecular weight be that 3000 Polyoxyethylene glycols form.
The preparation method of the cellulose base polyurethane sealing material described in this comparative example is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 80 DEG C, after 8g1-ethyl-3-methylimidazole bromine salt and 3g Mierocrystalline cellulose being mixed, be warming up to 110 DEG C, stir 2.5h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,100g polyether glycol is warming up to 115 DEG C, under vacuum tightness is 0.97MPa, stirs 2.5h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 20g tolylene diisocyanate is warming up to 65 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in described tolylene diisocyanate in 1h, then add 0.3g dibutyl tin laurate, be warming up to 90 DEG C, reaction 2h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1.5h, be cooled to 50 DEG C, obtain described cellulose base base polyurethane prepolymer for use as;
(2) preparation of B component
S4,32g silicon-dioxide to be dried at 110 DEG C, for subsequent use;
S5, at 50 DEG C, the silicon-dioxide after oven dry is added in 30g polyether glycol, stirring makes described polyoxytrimethylene triol, described Polyoxyethylene glycol and described silicon-dioxide Homogeneous phase mixing, 0.8g γ-aminopropyl triethoxysilane is dripped in the mixture obtained, stir, finally add 0.3g lead octoate 36,0.8g 2,6-ditertbutylparacresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, Keep agitation 50min, obtains described B component.
Comparative example 2
This comparative example provides a kind of cellulose base polyurethane sealing material, comprise cellulose base base polyurethane prepolymer for use as and B component, described cellulose base base polyurethane prepolymer for use as comprises component A, 70g polyether glycol, 20g tolylene diisocyanate and 0.3g dibutyl tin laurate; Wherein component A comprises 8g1-ethyl-3-methylimidazole bromine salt, 3g Mierocrystalline cellulose, 30g polyether glycol;
B component comprises 30g glycerine, 32g silicon-dioxide, 0.8g γ-aminopropyl triethoxysilane, 0.3g lead octoate 36,0.8g 2,6 ditertiary butyl p cresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole.
In this comparative example, the relative molecular weight that described polyether glycol is 3:1 by mass ratio be 5000 polyoxytrimethylene triol and relative molecular weight be that 3000 Polyoxyethylene glycols form.
The preparation method of the cellulose base polyurethane sealing material described in this comparative example is as follows:
(1) preparation of cellulose base base polyurethane prepolymer for use as
S1, at 80 DEG C, after 8g1-ethyl-3-methylimidazole bromine salt and 3g Mierocrystalline cellulose being mixed, add 30g polyether glycol wherein, and be warming up to 110 DEG C, stir 2.5h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2,70g polyether glycol is warming up to 115 DEG C, under vacuum tightness is 0.97MPa, stirs 2.5h, be then cooled to 60 DEG C, obtain the polyether glycol that dewaters, sealing saves backup;
S3, under nitrogen protection, 20g tolylene diisocyanate is warming up to 65 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in described tolylene diisocyanate in 1h, then add 0.3g dibutyl tin laurate, be warming up to 90 DEG C, reaction 2h, add the dehydrating mixt that described S1 is obtained again, continue reaction 1.5h, be cooled to 50 DEG C, obtain described cellulose base base polyurethane prepolymer for use as; (2) preparation of B component
S4,32g silicon-dioxide to be dried at 110 DEG C, for subsequent use;
S5, at 50 DEG C, the silicon-dioxide after oven dry is added in 30g glycerine, stirring makes described polyoxytrimethylene triol, described Polyoxyethylene glycol and described silicon-dioxide Homogeneous phase mixing, in the mixture obtained, drip 0.8g γ-aminopropyl triethoxysilane, stir, finally add 0.3g lead octoate 36,0.8g 2,6-ditertbutylparacresol and 0.5g 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, Keep agitation 50min, obtains described B component.
Carry out physical and mechanical property test to the cellulose base polyurethane sealing material of above-mentioned preparation, result is as shown in table 1.
Table 1
In addition, at above-mentioned sealing material is placed in 80 DEG C, keep 168h, 150% stretches, the determining of cellulose base polyurethane sealing material described in embodiment 1-5 stretches cohesiveness without destruction, and comparative example 1 and the cellulose base polyurethane sealing material described in comparative example 2 determine stretch cohesiveness and all have destruction; After above-mentioned three kinds of sealing materials immersion 96h, 150% stretches, the determining of cellulose base polyurethane sealing material described in embodiment 1-5 stretches cohesiveness without destruction, and comparative example 1 and the cellulose base polyurethane sealing material described in comparative example 2 determine stretch cohesiveness and all have destruction; To above-mentioned sealing material thermal ageing process 168h at 80 DEG C, the stretching strength retentivity of the cellulose base polyurethane sealing material described in embodiment 1-5 and elongation at break conservation rate >=80, the stretching strength retentivity of the cellulose base polyurethane sealing material described in comparative example 1 and elongation at break conservation rate >=70, the stretching strength retentivity of the cellulose base polyurethane sealing material described in comparative example 2 and elongation at break conservation rate >=70; After above-mentioned sealing material alkaline purification 168h, the stretching strength retentivity of the cellulose base polyurethane sealing material described in embodiment 1-5 and elongation at break conservation rate >=80, the stretching strength retentivity of the cellulose base polyurethane sealing material described in comparative example 1 and elongation at break conservation rate >=60, the stretching strength retentivity of the cellulose base polyurethane sealing material described in comparative example 2 and elongation at break conservation rate >=70.
As can be seen from above-mentioned physical and mechanical property test result, cellulose base polyurethane sealing material hardness of the present invention is low, good springiness, high tensile is maintained while possessing low modulus, and still can good cohesiveness be kept under the condition of high temperature, high humidity, also there is good alkali resistance and ultraviolet aging resistance simultaneously.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (15)
1. a cellulose base base polyurethane prepolymer for use as, is characterized in that,
Comprise component A, 60-80 weight part polyether glycol, 10-25 weight part isocyanic ester, described component A comprises 5-12 weight part ionic liquid, 1-5 part by weight of cellulose and 20-40 weight part polyether glycol.
2. cellulose base base polyurethane prepolymer for use as according to claim 1, is characterized in that,
Described polyether glycol is the trivalent alcohol of mass ratio 2:1-4.5:1 and the mixture of dibasic alcohol formation.
3. cellulose base base polyurethane prepolymer for use as according to claim 2, is characterized in that, the relative molecular weight of described trivalent alcohol is 4000-6000, and the relative molecular weight of described dibasic alcohol is 2000-4000.
4. cellulose base base polyurethane prepolymer for use as according to claim 3, is characterized in that,
Described dibasic alcohol is one or more in Polyoxyethylene glycol, polyoxypropyleneglycol, polytetrahydrofuran diol, and described trivalent alcohol is one or more in polyoxytrimethylene triol, oxypropylene-oxyethylene copolyether triol, Viscotrol C.
5. according to the arbitrary described cellulose base base polyurethane prepolymer for use as of claim 1-4, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-allyl group-3-Methylimidazole villaumite, 1-butyl-3-Methylimidazole villaumite or 1-vinyl-3-butyl imidazole villaumite.
6. according to the arbitrary described cellulose base base polyurethane prepolymer for use as of right 1-5, it is characterized in that, described isocyanic ester is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate.
7., according to the arbitrary described cellulose base base polyurethane prepolymer for use as of claim 1-6, it is characterized in that, also comprise the promotor of 0.05-0.5 weight part, described promotor is dibutyl tin laurate or triethylamine.
8. one kind comprises the sealing material of the arbitrary described cellulose base base polyurethane prepolymer for use as of claim 1-7, it is characterized in that, also comprise B component, described B component comprises polyether glycol described in 20-40 weight part, 15-50 parts of filler material by weight, 0.2-1.5 weight part coupling agent, 0.1-0.5 part by weight of catalyst, 0.2-1.5 weight part oxidation inhibitor and 0.1-1 weight part uv-absorbing agent.
9. sealing material according to claim 8, is characterized in that, described filler is one or more in silicon-dioxide, calcium carbonate, calcium oxide, flyash, talcum powder, kaolin, carbon black and titanium dioxide.
10. sealing material according to claim 9, is characterized in that, described coupling agent is γ-aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane;
Described catalyzer is lead octoate 36, stannous octoate, dibutyl tin laurate, N-ethylmorpholine or N, N-dimethylcyclohexylamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol or four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described uv-absorbing agent be 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3-dodecyl-5-methyl) benzotriazole, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole or 2-(3 ', 5 '-two tert-pentyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole.
11.-10 arbitrary described sealing materials according to Claim 8, it is characterized in that, the mass ratio of described cellulose base base polyurethane prepolymer for use as and described B component is 3:1.
12. 1 kinds of methods preparing the arbitrary described sealing material of claim 8-11, comprise the steps:
(1) preparation of cellulose base base polyurethane prepolymer for use as
At S1,60-100 DEG C, after desired ion liquid and Mierocrystalline cellulose being mixed, add a certain amount of polyether glycol wherein, and be warming up to 105-120 DEG C, stir 2-3h, be cooled to 60 DEG C, obtain dehydrating mixt, described dehydrating mixt sealing is preserved, for subsequent use;
S2, general more a certain amount of polyether polyols dehydration of alcohols obtain the polyether glycol that dewaters, and sealing saves backup;
S3, under nitrogen protection, isocyanic ester is warming up to 60-70 DEG C, the dehydration polyether glycol prepared in described S2 is dropped in isocyanic ester in 1h, be warming up to 80-100 DEG C, reaction 1-3h, then add the obtained dehydrating mixt of described S1, continue reaction 1-2h, be cooled to 40-60 DEG C, obtain described component A;
(2) preparation of B component
S4, described filler to be dried at 105-115 DEG C, for subsequent use;
S5, at 40-60 DEG C, the described filler after oven dry is added in a certain amount of polyether glycol again, stirring makes described polyether glycol mix with uniform filling, coupling agent is dripped in the mixture obtained, stir, finally add catalyzer, oxidation inhibitor and uv-absorbing agent, Keep agitation 0.5-1h, obtain described B component.
13. methods preparing sealing material according to claim 12, is characterized in that, also comprise the step adding promotor in described step S3.
14. methods preparing sealing material according to claim 12, is characterized in that,
Described step S2, for a certain amount of polyether glycol is warming up to 110-120 DEG C, under vacuum tightness is 0.097MPa, stirs 2-3h, is then cooled to 60 DEG C, obtains the polyether glycol after dewatering.
The arbitrary described sealing material of 15. claim 8-11 concrete structure, highway, bridge, airstrip seam and glass is installed, electron device filling in application.
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