Background technology
End-silicane-group urethane is as a kind of novel macromolecular material and the raw material of tackiness agent and seal gum, and is more and more noticeable.End-silicane-group urethane compatibility the advantage of silicone sealant and polyurethane sealant, can at room temperature solidify by moisture in the air, can be during curing because of not emitting CO
2And foamed phenomenon appears, over-all properties is more excellent, has very big market potential.
Organic silicone polyurethane copolymer is a class novel high polymer material, from the molecule segment structure, it had both contained excellent dielectricity, snappiness, water tolerance, the organosilicon segment of ventilation property and biocompatibility, has simultaneously good thermostability again, the urethane segment of weathering resistance and wear resistance, therefore, a certain amount of hydroxy-terminated polysiloxane of interpolation copolymerization in end-silicane-group urethane synthetic, the advantage of compatible organosilicon and polyurethane material helps further to improve the snappiness of material and weather-proof, water-fast, resistant to chemical media, anti-fuel oil and characteristic such as heat-resisting.
Usually needing when the end-silicane-group base polyurethane prepolymer for use as is used as seal gum to add reinforced filling, mainly is water-ground limestone and light calcium carbonate and wherein use more filler, can not strengthen simultaneously with toughness reinforcing usually but introduce filler.In recent years, nano-intercalation technology is widely used in polyurethane-modified technology.Nano intercalated modification is to improve one of effective means of material mechanical performance, particularly toughness, can realize simultaneously strengthening and toughening effect, can also increase substantially thermostability, flame retardant resistance and the barrier etc. of polymkeric substance in addition.Many polymkeric substance can with laminar silicic acid salt formation nano composite material, as nylon 6, urethane, Resins, epoxy, polystyrene, polyester, polypropylene, paracril, styrene-butadiene rubber(SBR), silicon rubber etc.Also do not meet report at present and use nano layered silicate and end-silicane-group urethane to form nano composite material.
Open day is on March 16th, 2005, publication number is CN 1594480A, and name is called and discloses the seal gum that contains following mass percent component in the Chinese patent application of " a kind of silicane-modified polyurethane joint sealant and preparation method thereof ": end hydroxy polyether 20~45, isocyanic ester 3~10, softening agent 15~38, mineral filler 15~50, silane coupling agent 0.01~0.1, catalyzer 0.01~0.3, oxidation inhibitor 0.01~0.2.
Open day is on January 11st, 2006, publication number is CN 1718663A, name is called and discloses the seal gum that contains following mass percent component in the Chinese patent application of " a kind of monocomponent moisture cure siloxane modified polyurethane sealant and preparation method thereof ": softening agent 15~30, ditan two isocyanides 3~10, polyethers 10~30, calcium oxide 1~4, water-retaining agent 0.2~0.5, carbon black 10~20, lime carbonate 10~20, silica 1~5, silane coupling agent KH550 0.1~0.4, isophorone diisocyanate 0.1~2, silane coupling agent KH560 0.2~0.6, dibutyl tin laurate 0.01~0.04, α, ω-two (4-hydroxyl butyl) polydimethylsiloxane 5~12, two woods Anaesthetie Ethers 0.1~0.4.
Disclosed seal gum does not all have and adopts organosilicon copolymerization and applying nano intercalation technique that seal gum is carried out modification simultaneously in the preparation in the above-mentioned patent application, and the seal gum of its preparation is when the strength of materials improves, and elasticity-elongation at break can produce decline.
Summary of the invention
The objective of the invention is for overcoming the above-mentioned shortcoming and defect of existing seal gum, provide a kind of composite modified by nano organic montmorillonite and organosilicon, have good snappiness, wear resistance, cementability, and solvent-free, environmentally safe, to the nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum of human body toxicological harmless, the present invention also provides the preparation method of this seal gum simultaneously.
Nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum provided by the present invention comprises the component of following weight part:
100 parts of modified end-silicane-group organosilicon polyether(poly)urethanes
5~20 parts of nano organic montmorillonites
5~150 parts of mineral fillers
0.2~1.5 part of catalyzer
For better realization the present invention,
The modified end-silicane-group organosilicon polyether(poly)urethane that described modified end-silicane-group organosilicon polyether(poly)urethane is preferably made by following method:
Get the raw material of following weight part:
100 parts of end hydroxy polyethers
5~20 parts of vulcabond
0~15 part of hydroxy-terminated polysiloxane
2~15 parts of silane coupling agents
Hydroxy-terminated polysiloxane and end hydroxy polyether dehydration back are mixed with vulcabond, and under vacuum environment, controlled temperature reacted 5 hours down at 65 ℃~95 ℃, was prepared into the base polyurethane prepolymer for use as of isocyanate terminated base earlier; Add silane coupling agent again,, reacted 0.5~2 hour down, be prepared into silicane-group organosilicon modified polyether type polyurethane at 60 ℃~80 ℃ according to the difference of silane coupling agent.
The following polyether glycol of wherein said end hydroxy polyether preferred molecular weight between 300~6000: the mixture of a kind of or two kinds of compositions in polyoxypropyleneglycol or the polyoxytrimethylene triol;
The preferred tolylene diisocyanate of described vulcabond, ditan-4,4 '-vulcabond or isophorone diisocyanate;
The preferred α of described hydroxy-terminated polysiloxane, alpha, omega-dihydroxy polydimethyl siloxane, molecular weight are 400~100000;
Described silane coupling agent is preferably as follows the amino functional silane of end: γ-An Bingjisanyiyangjiguiwan, anilinomethyl triethoxysilane, N-phenyl-γ-An Bingjisanjiayangjiguiwan or N-ethyl trimethoxy silicon-2-methyl-propyl amine.
The nano organic montmorillonite that the preferred following method of described nano organic montmorillonite makes:
(1) with cation exchange capacity 1~40 part of the polynite of 50~200mmol/100g, at 50~2000 parts of deionized water for stirring 0.5~8h;
(2) 0.1~20 part of cationite is added in 20~800 parts of deionized waters, add 0.1~50 part of protonating agent again, be heated to 50~80 ℃;
(3) stirring mixes step (1), (2) gained solution down, and precipitation is filtered, and vacuum-drying is also fully pulverized and obtained nano organic montmorillonite;
Described cationite be 12 to octadecyl trimethylammonium quaternary amine or 12 to octadecyl triethyl quaternary amine; Wherein said protonating agent is hydrochloric acid, sulfuric acid or nitric acid; Described part all is meant weight part.
The preferred nm-class active calcium carbonate of described mineral filler, nano silicon, 100~5000 purpose silicon-dioxide or lime carbonate.
Described catalyzer is preferably as follows the organic tin compound: dibutyl tin laurate or stannous octoate.
The preparation method of nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum of the present invention may further comprise the steps:
(1) silicane-group organosilicon modified polyether type polyurethane is synthetic,
Get the raw material of following weight part:
100 parts of end hydroxy polyethers
5~20 parts of vulcabond
0~15 part of hydroxy-terminated polysiloxane
2~15 parts of silane coupling agents
Hydroxy-terminated polysiloxane and end hydroxy polyether dehydration back are mixed with vulcabond, and under vacuum environment, controlled temperature reacted 5 hours down at 65 ℃~95 ℃, was prepared into the base polyurethane prepolymer for use as of isocyanate terminated base earlier; Add silane coupling agent again,, reacted 0.5~2 hour down, be prepared into silicane-group organosilicon modified polyether type polyurethane at 60 ℃~80 ℃ according to the difference of silane coupling agent;
(2) take off the row component by weight:
100 parts of the modified end-silicane-group organosilicon polyether(poly)urethanes that step (1) makes
5~20 parts of nano organic montmorillonites
5~150 parts of mineral fillers
0.2~1.5 part of catalyzer
After the silicane-group organosilicon modified polyether type polyurethane that step (1) is made and the nano organic montmorillonite of drying mix, use mechanical mill again, obtain the end-silicane-group urethane of nano organic montmorillonite modification;
(3) the end-silicane-group urethane of the nano organic montmorillonite modification that step (2) is made again with mineral filler, catalyst mix, stir, obtain nano organic montmorillonite modified end-silicane-group organosilicon modified polyurethane type seal gum.
The following polyether glycol of end hydroxy polyether preferred molecular weight described in the described step (1) between 300~6000: the mixture of a kind of or two kinds of compositions in polyoxypropyleneglycol or the polyoxytrimethylene triol;
The preferred tolylene diisocyanate of vulcabond described in the described step (1), ditan-4,4 '-vulcabond or isophorone diisocyanate;
The preferred α of hydroxy-terminated polysiloxane described in the described step (1), alpha, omega-dihydroxy polydimethyl siloxane, molecular weight are 400~100000;
Silane coupling agent described in the described step (1) is preferably as follows the amino functional silane of end: γ-An Bingjisanyiyangjiguiwan, anilinomethyl triethoxysilane, N-phenyl-γ-An Bingjisanjiayangjiguiwan or N-ethyl trimethoxy silicon-2-methyl-propyl amine.
Mineral filler described in the described step (2) comprises nm-class active calcium carbonate, nano silicon, 100~5000 purpose silicon-dioxide or lime carbonate;
Catalyzer described in the described step (2) comprises following organic tin compound: dibutyl tin laurate or stannous octoate.
The nano organic montmorillonite that nano organic montmorillonite is preferably made by following method described in the described step (2):
(1) with cation exchange capacity 1~40 part of the polynite of 50~200mmol/100g, at 50~2000 parts of deionized water for stirring 0.5~8h;
(2) 0.1~20 part of cationite is added in 20~800 parts of deionized waters, add 0.1~50 part of protonating agent again, be heated to 50~80 ℃;
(3) stirring mixes step (1), (2) gained solution down, and precipitation is filtered, and vacuum-drying is also fully pulverized and obtained nano organic montmorillonite;
Described cationite be 12 to octadecyl trimethylammonium quaternary amine or 12 to octadecyl triethyl quaternary amine; Wherein said protonating agent is hydrochloric acid, sulfuric acid or nitric acid; Described part all is meant weight part.
Stirring in the preparation nano organic montmorillonite is in order to make polynite and cationite blending dispersion in deionized water even.The speed that stirs is 30~2000 rev/mins and all can realizes purpose of the present invention.
Compared with prior art, the present invention has following main useful technique effect:
(1) the nano organic montmorillonite intercalation technique is incorporated in the preparation of end-silicane-group polyurethane sealant, because the strong interfacial interaction between nano organic montmorillonite and the polymeric matrix realizes that simultaneously the end-silicane-group polyurethane sealant strengthens and toughness reinforcing effect.
Below listed in the table one through the performance physical and chemical parameter contrast of nano organic montmorillonite modification with the end-silicane-group polyurethane sealant that does not add polynite:
The mechanical property of table one, nano organic montmorillonite modification end-silicane-group polyurethane type seal gum
Add the polynite ratio |
0 |
5% |
10% |
15% |
Add the mineral filler ratio |
100% |
100% |
100% |
20% |
Hardness (Shao Shi A) |
23 |
32 |
37 |
38 |
Tensile strength (MPa) |
0.65 |
1.55 |
2.00 |
2.03 |
Elongation at break (%) |
208 |
271 |
259 |
233 |
Annotate: feed composition and ratio that the listed seal gum of this table adopts are 8 parts of tolylene diisocyanates, 100 parts of 330N polyethers, 8.5 parts of N-phenyl-γ-An Bingjisanjiayangjiguiwans, and the mineral filler of being added is 300 order lime carbonate; Above-mentioned hardness is by the test of Shao Shi durometer, and tensile strength and elongation at break are tested by the method for GB/T528 standard code.
By in the table one as seen, end-silicane-group polyurethane sealant through the nano organic montmorillonite modification, particularly when the addition of nano organic montmorillonite 5%~10% the time, its tensile strength and elongation at break do not add all being greatly improved of polynite, have shown that fully technology of the present invention improves effect.
(2) in end-silicane-group urethane synthetic, introduced hydroxy-terminated polysiloxane, its terminal hydroxy group active group and the reaction of isocyano group, thereby in polyurethane chain, introduced siloxane groups, make it have the advantage of polysiloxane and urethane concurrently, form unique network structure through end of the chain organoalkoxysilane hydrolysis after simultaneously, make seal gum have higher mechanical strength and elongation simultaneously.
Below list the performance physical and chemical parameter of the nano organic montmorillonite modification end-silicane-group polyurethane type seal gum that adds the hydroxy-terminated polysiloxane preparation in the table two:
Table two, the mechanical property of adding the nano organic montmorillonite modification end-silicane-group polyurethane type seal gum of hydroxy-terminated polysiloxane preparation
Add the hydroxy-terminated polysiloxane ratio |
0 |
5% |
10% |
15% |
Add the nano organic montmorillonite ratio |
5% |
5% |
5% |
5% |
Add the mineral filler ratio |
50% |
50% |
50% |
50% |
Hardness (Shao Shi A) |
34 |
32 |
30 |
37 |
Tensile strength (MPa) |
1.30 |
1.30 |
1.24 |
1.06 |
Elongation at break (%) |
267 |
306 |
289 |
263 |
Annotate: raw material and ratio that the listed seal gum of this table adopts are ditan-4,12 parts of 15 parts of 4 '-vulcabond, 100 parts of N220 polyethers, N-ethyl trimethoxy silicon-2-methyl-propyl amine, the α that is added, the alpha, omega-dihydroxy polydimethyl siloxane molecular weight is 12000, and the mineral filler of being added is nm-class active calcium carbonate; Above-mentioned hardness is by the test of Shao Shi durometer, and tensile strength and elongation at break are tested by the method for GB/T528 standard code.
By table two as can be seen, in adding the organic imvite modified seal gum of same ratio, add the seal gum of hydroxy-terminated polysiloxane preparation, particularly when the addition of hydroxy-terminated polysiloxane 5%~10% the time, seal gum is when keeping high tensile, the seal gum that makes its elongation at break not add hydroxy-terminated polysiloxane again has the raising of higher degree, has shown that fully technology of the present invention improves effect.
(3) the present invention does not add organic solvent, so also have environmentally safe, to the advantage of human body toxicological harmless.
Embodiment
Further specify the present invention below in conjunction with embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
After the N220 polyethers dehydration with 240g, mix with the tolylene diisocyanate (TDI) of 27.2g, reaction is 5 hours under 90 ℃, vacuum environment, be prepared into base polyurethane prepolymer for use as, add silane coupling agent N-phenyl-γ-An Bingjisanjiayangjiguiwan 18.5g again, reacted 2 hours down at 80 ℃, be prepared into end-silicane-group urethane; The nano organic montmorillonite of 14.3g is joined in the above-mentioned end-silicane-group urethane, and back mechanical mill stirs; Again 343g 800 order silicon-dioxide, 2.8g dibutyl tin laurate are joined in the end-silicane-group urethane of nano organic montmorillonite modification, stir, obtain nano organic montmorillonite modification end-silicane-group polyurethane type seal gum.The hardness of gained seal gum is 32, and tensile strength is 0.74MPa, and elongation at break is 241%.
Embodiment 2
α with 21.8g, after the 330N polyethers of alpha, omega-dihydroxy polydimethyl siloxane, 265g and the dehydration of the N220 polyethers of 102g, ditan-4 with 49.5g, 4 '-vulcabond (MDI) mixes, reaction is 5 hours under 95 ℃, vacuum environment, is prepared into base polyurethane prepolymer for use as, adds silane coupling agent N-phenyl-γ-An Bingjisanjiayangjiguiwan 33.7g again, reacted 2 hours down at 80 ℃, be prepared into end-silicane-group urethane; The nano organic montmorillonite of 52.5g is joined in the above-mentioned end-silicane-group urethane, and back mechanical mill stirs; Again 26.3g nano silicon, 5.3g dibutyl tin laurate are joined in the end-silicane-group urethane of nano organic montmorillonite modification, stir, obtain nano organic montmorillonite modification end-silicane-group polyurethane type seal gum.The hardness of gained seal gum is 34, and tensile strength is 1.19MPa, and elongation at break is 270%.
Embodiment 3
α with 16g, after the N210 polyethers dehydration of alpha, omega-dihydroxy polydimethyl siloxane and 200g, mix with the isophorone diisocyanate (IPDI) of 53.3g, reaction is 5 hours under 90 ℃, vacuum environment, be prepared into base polyurethane prepolymer for use as, add silane coupling agent anilinomethyl triethoxysilane 21.5g again, reacted 2 hours down, be prepared into end-silicane-group urethane at 80 ℃; The nano organic montmorillonite of 101g is joined in the above-mentioned end-silicane-group urethane, and back mechanical mill stirs; Again 251g300 purpose lime carbonate, 6.2g stannous octoate are joined in the end-silicane-group urethane of nano organic montmorillonite modification, stir, obtain nano organic montmorillonite modification end-silicane-group polyurethane type seal gum.The hardness of gained seal gum is 42, and tensile strength is 1.65MPa, and elongation at break is 203%.
Embodiment 4
α with 34.8g, after the 330N polyethers dehydration of alpha, omega-dihydroxy polydimethyl siloxane and 435g, mix with the tolylene diisocyanate (TDI) of 29.4g, reaction is 5 hours under 95 ℃, vacuum environment, be prepared into base polyurethane prepolymer for use as, add silane coupling agent N-ethyl trimethoxy silicon-2-methyl-propyl amine 15.7g again, reacted 1.5 hours down, be prepared into end-silicane-group urethane at 80 ℃; The nano organic montmorillonite of 25.8g is joined in the above-mentioned end-silicane-group urethane, and back mechanical mill stirs; Again 378g nm-class active calcium carbonate, 8.1g dibutyl tin laurate are joined in the end-silicane-group urethane of nano organic montmorillonite modification, stir, obtain nano organic montmorillonite modification end-silicane-group polyurethane type seal gum.The hardness of gained seal gum is 32, and tensile strength is 1.24MPa, and elongation at break is 302%.
Embodiment 5
After the N330 polyethers dehydration with the N210 polyethers of 75g and 150g, ditan-4 with 45.2g, 4 '-vulcabond (MDI) mixes, reaction is 5 hours under 90 ℃, vacuum environment, be prepared into base polyurethane prepolymer for use as, add silane coupling agent γ-An Bingjisanyiyangjiguiwan 17.6g again, reacted 0.5 hour down, be prepared into end-silicane-group urethane at 75 ℃; The nano organic montmorillonite of 72.5g is joined in the above-mentioned end-silicane-group urethane, and back mechanical mill stirs; Again 96.6g nm-class active calcium carbonate, 4.8g stannous octoate are joined in the end-silicane-group urethane of nano organic montmorillonite modification, stir, obtain nano organic montmorillonite modification end-silicane-group polyurethane type seal gum.The hardness of gained seal gum is 38, and tensile strength is 2.03MPa, and elongation at break is 243%.