CN105820551A - Antiaging polyurethane composite material - Google Patents

Antiaging polyurethane composite material Download PDF

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CN105820551A
CN105820551A CN201610249133.1A CN201610249133A CN105820551A CN 105820551 A CN105820551 A CN 105820551A CN 201610249133 A CN201610249133 A CN 201610249133A CN 105820551 A CN105820551 A CN 105820551A
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parts
weight
hydroxyl
butyl
hydroxy
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龚文祥
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Chuzhou Huanqiu Polyurethane Technology Co Ltd
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Chuzhou Huanqiu Polyurethane Technology Co Ltd
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    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract

The invention discloses an antiaging polyurethane composite material which is prepared from polyoxypropylene diol, hydroxyl-terminated liquid silicone rubber, hydroxyl-terminated liquid nitrile-butadiene rubber, 1,4-cyclohexane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-butynediol, 1,4-di(2-hydroxyethoxy)benzene, 4,4'-diaminodiphenyl sulfone, dibutyltin dilaurate, bis dodecyldimethyl ammonium bromide, graphene oxide, carbon nanotubes, hydroxy polydimethylsiloxane, a heat stabilizer, polystyrene and a rare-earth complex. The heat stabilizer is prepared from nano titanium dioxide, molybdenum trioxide, bismuth trioxide, triglycol bis-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], pentaerythritol diisodecyl diphosphite, monophenyldiisodecyl phosphite and ethyl 2,2'-thiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

Description

A kind of weather-resistant pu composite
Technical field
The present invention relates to polyurethanes technology field, particularly relate to a kind of weather-resistant pu composite.
Background technology
Polyurethane is formed, greatly with dihydroxy or polyol addition polymerization by diisocyanate or polyisocyanates In molecule in addition to carbamate, possibly together with the groups such as ether, ester, urea, biuret, allophanate, knot Structure change is a lot, is widely used at a lot of aspects at present, such as can substitute for rubber, plastics, Nylon etc., for airport, hotel, building materials, automobile factory, colliery factory, cement plant, condo, villa, The fields such as landscaping, colored stone art, park.But the weatherability of polyurethane is poor, when using out of doors Easily there is the catabiosis such as yellowing, be full of cracks, severely impact outward appearance and the mechanical property of goods.
Summary of the invention
The technical problem existed based on background technology, the present invention proposes a kind of weather-resistant pu composite, Its intensity is high, and thermostability and ageing-resistant performance are excellent, can meet the use requirement of multiple fields.
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 45-65 part, terminal hydroxy liquid silicone rubber 5-20 part, hydroxyl terminated butyl nitrile (HTBN) rubber 5-20 part, 1,4- Cyclohexane diisocyanate 10-25 part, 1,5-naphthalene diisocyanate 5-25 part, 1,4-butynediols 2-6 part, 1,4-bis-(2-hydroxyl-oxethyl) benzene 1-5 part, 4,4 '-benzidine sulfone 2-5 part, di lauric dibutyl Stannum 0.01-0.15 part, didodecyldimethylammbromide bromide 1-5 part, graphene oxide 2-10 part, carbon nanometer Pipe 2-10 part, hydroxyl polydimethylsiloxane 3-12 part, heat stabilizer 3-15 part, polystyrene 2-10 part, Rare earth compounding 3-8 part；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 2-15 part, three oxidations Molybdenum 2-15 part, bismuth oxide 1-8 part, 2,2'-ethylenedioxybis(ethanol). pair-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) third Acid esters] 1-10 part, diphosphorous acid tetramethylolmethane two isodecyl ester 1-8 part, phosphorous acid one benzene two isodecyl ester 2-15 part, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 2-10 part.
Preferably, in its raw material, polyoxypropyleneglycol, terminal hydroxy liquid silicone rubber, terminal hydroxy liquid fourth Nitrile rubber, 1,4-cyclohexane diisocyanate, the weight ratio of 1,5-naphthalene diisocyanate are 50-62:11-18: 9-18:15-22:11-22.
Preferably, its raw material includes by weight: polyoxypropyleneglycol 55-60 part, terminal hydroxy liquid silicon rubber Glue 12-15 part, hydroxyl terminated butyl nitrile (HTBN) rubber 11-17 part, 1,4-cyclohexane diisocyanate 18-21 part, 1,5- Naphthalene diisocyanate 15-20 part, 1,4-butynediols 3.5-4.2 part, 1,4-bis-(2-hydroxyl-oxethyl) benzene 3-3.8 part, 4,4 '-benzidine sulfone 3-3.8 part, dibutyl tin laurate 0.05-0.12 part, double ten Dialkyl dimethyl ammonium bromide 3.2-4 part, graphene oxide 5.5-6.5 part, CNT 5.8-7 part, hydroxyl Polydimethylsiloxane 6-10 part, heat stabilizer 10-12.5 part, polystyrene 5.8-6.5 part, rare earth coordinate Thing 5-7 part.
Preferably, its raw material includes by weight: polyoxypropyleneglycol 58 parts, terminal hydroxy liquid silicone rubber 13.5 parts, hydroxyl terminated butyl nitrile (HTBN) rubber 16 parts, 1,4-cyclohexane diisocyanate 20 parts, 1,5-naphthalene two different Cyanate 17 parts, 1,4-butynediols 4 parts, 1,4-bis-(2-hydroxyl-oxethyl) benzene 3.6 parts, 4,4 '-diamino Base biphenyl sulfone 3.2 parts, dibutyl tin laurate 0.1 part, didodecyldimethylammbromide bromide 3.7 parts, oxygen Functionalized graphene 6 parts, CNT 6.3 parts, hydroxyl polydimethylsiloxane 7.5 parts, heat stabilizer 11 parts, poly- Styrene 6.2 parts, rare earth compounding 6.5 parts.
Preferably, its raw material of described heat stabilizer includes by weight: nano titanium oxide 8-13 part, three oxygen Change molybdenum 8-11 part, bismuth oxide 3.5-6.2 part, 2,2'-ethylenedioxybis(ethanol). pair-[3-(3-tertiary butyl-4-hydroxy-5-methyl Phenyl) propionic ester] 5.8-7 part, diphosphorous acid tetramethylolmethane two isodecyl ester 4.5-6 part, phosphorous acid one benzene two is different The last of the ten Heavenly stems ester 8-10 part, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 5.5-8.5 Part.
Preferably, its raw material of described heat stabilizer includes by weight: nano titanium oxide 10 parts, three oxidations Molybdenum 10 parts, bismuth oxide 6 parts, 2,2'-ethylenedioxybis(ethanol). be double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propanoic acid Ester] 6.2 parts, diphosphorous acid tetramethylolmethane two isodecyl ester 5.2 parts, phosphorous acid one benzene two isodecyl ester 8.6 parts, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 7 parts.
Preferably, described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight 20-50 part polyvinyl alcohol, 0.8-2 part isopropanolamine are added in 100 parts of acetonitriles by amount part, stir at 65-75 DEG C Mix and uniformly obtain solution A；By weight nitroxyl chloride phenyl formate is dissolved in 30-50 part acetonitrile by 3-8 part and obtaining Solution B；At 5-10 DEG C, by weight 35-50 part solution B is added in 120-150 part solution A, then stir Mixing reaction 15-20h, freezing 5-10h in refrigerator is put in reaction after terminating, through filtration, evaporation, precipitating, drying Obtain modified polyvinylalcohol；By weight 20-50 part chitosan is dissolved in 100 parts of deionized waters, at 55-70 DEG C It is cooled to room temperature after lower stirring 30-50min, is subsequently adding 5-12 part modified polyvinylalcohol, stirs at 30-35 DEG C Mix 20-35h, stirring terminate after through dialysis, rotary evaporation, be dried to obtain grafting polyvinyl alcohol；By weight 1.5-3 part grafting polyvinyl alcohol is added in 100 parts of deionized waters, add 0.2-0.5 part Europium chloride, 0.1-0.5 Part lanthanum chloride, then the pH value of regulation system is neutral, reacts 20-30min at 75-85 DEG C, and reaction terminates Described rare earth compounding is obtained by dialysing, be dried, grinding.
Preferably, described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight 35 parts of polyvinyl alcohol, 1.3 parts of isopropanolamines are added in 100 parts of acetonitriles by amount part, stir at 70 DEG C To solution A；By weight nitroxyl chloride phenyl formate is dissolved in 42 parts of acetonitriles by 6.5 parts and obtains solution B；At 8 DEG C Under, by weight 43 parts of solution B are added in 140 parts of solution A, then stirring reaction 17.5h, reaction terminates After put in refrigerator freezing 8.5h, obtain modified polyvinylalcohol through filtration, evaporation, precipitating, drying；By weight 35 parts of chitosans are dissolved in 100 parts of deionized waters by amount part, are cooled to room temperature after stirring 40min at 65 DEG C, Be subsequently adding 10 parts of modified polyvinylalcohols, at 33 DEG C stir 28h, stirring terminate after through dialysis, rotary evaporation, It is dried to obtain grafting polyvinyl alcohol；By weight 2.8 parts of grafting polyvinyl alcohols are added in 100 parts of deionized waters, Adding 0.35 part of Europium chloride, 0.35 part of lanthanum chloride, then the pH value of regulation system is neutral, anti-at 80 DEG C Described rare earth compounding is obtained through dialysing, be dried, grinding after answering 26min, reaction to terminate；At rare earth compounding Preparation process in, first, have selected and polyvinyl alcohol is activated by nitroxyl chloride phenyl formate, it is right to make Chlorine in nitroxyl chloride phenyl formate there occurs reaction with the hydroxyl in polyvinyl alcohol, has obtained modified polyvinylalcohol, After adding chitosan, the amino in chitosan can be had an effect with modified polyvinylalcohol, sloughs from molecule Paranitrophenol, has obtained grafting polyvinyl alcohol, after it is mixed with Europium chloride and lanthanum chloride, and europium and lanthanum energy Oxygen atom generation coordination with grafting polyvinyl alcohol, has obtained rare earth compounding, has been added into system In, on the one hand, with graphene oxide, CNT, nano titanium oxide, molybdenum trioxide and three oxidations two Bismuth has synergism, significantly improves the intensity of composite, on the other hand, with terminal hydroxy liquid silicon rubber Glue, 1,4-butynediols, 1,4-bis-(2-hydroxyl-oxethyl) benzene, 4,4 '-benzidine sulfone, hydroxyl are poly- Dimethyl siloxane, heat stabilizer, polystyrene coordinate, and significantly improve the thermostability of composite, resistance to Aqueous and resistance to ag(e)ing.
Weather-resistant pu composite of the present invention can prepare work according to conventional compound polyurethane material Skill is prepared from.
Weather-resistant pu composite of the present invention, with polyoxypropyleneglycol, terminal hydroxy liquid silicon rubber Glue, hydroxyl terminated butyl nitrile (HTBN) rubber, 1,4-cyclohexane diisocyanate and 1,5-naphthalene diisocyanate are poly-ammonia Ester monomer, the polyurethane obtained have brilliance physical property, have simultaneously excellence thermostability, tolerance to cold, Electrical insulating property and resistance to ag(e)ing；In Isosorbide-5-Nitrae-butynediols addition system, three keys therein can be anti-by heat cross-linking The network structure that intermolecular highly cross-linked formation is more stable should be made, with Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene, 4,4 '-benzidine sulfone, as chain extender, significantly improves thermostability and the resistance to ag(e)ing of composite； Didodecyldimethylammbromide bromide in system can form new change with the functional group of remnants on graphene oxide Learn key, thus at the surface grafting long alkyl chain of Graphene, be uniformly dispersed in system, be simultaneously introduced CNT can be attached at the surface of graphene oxide, thus is connected to the graphene sheet layer in different spaces orientation, Play function served as bridge to run through or between cincture and graphene sheet layer, during polyurethane is heated, himself Aromatic conjugated structure can catch and couple produced free radical when polyurethane decomposes, thus effectively hinder poly- The further decomposition of urethane strand, significantly improves resistance to ag(e)ing and the thermostability of composite, it addition, After it is worked in coordination with the nano titanium oxide in heat stabilizer, molybdenum trioxide, bismuth oxide, significantly improve The intensity of composite；In heat stabilizer, with nano titanium oxide, molybdenum trioxide, bismuth oxide, three Glycol pair-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], diphosphorous acid tetramethylolmethane two isodecyl Ester, phosphorous acid one benzene two isodecyl ester, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid Ethyl ester] it is raw material, give the excellent thermostability of composite and resistance to ag(e)ing after working in coordination with, improve compound simultaneously The mechanical strength of material, resistance to water and stability, the hydroxyl polydimethylsiloxane of addition, polystyrene and Rare earth compounding and heat stabilizer also have synergism, significantly improve composite thermostability and resistance to always The property changed.
Detailed description of the invention
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 65 parts, 5 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 20 parts, 1,4-hexamethylene Diisocyanate 10 parts, 1,5-naphthalene diisocyanate 25 parts, 1,4-butynediols 2 parts, 1,4-bis-(2-hydroxyl Ethyoxyl) benzene 5 parts, 4,4 '-benzidine sulfone 2 parts, dibutyl tin laurate 0.15 part, double dodecane Base ditallowdimethyl ammonium bromide 1 part, graphene oxide 10 parts, CNT 10 parts, hydroxyl polydimethylsiloxane 3 Part, heat stabilizer 15 parts, polystyrene 2 parts, rare earth compounding 8 parts；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 2 parts, molybdenum trioxide 15 Part, bismuth oxide 1 part, 2,2'-ethylenedioxybis(ethanol). be double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] 10 Part, diphosphorous acid tetramethylolmethane two isodecyl ester 1 part, phosphorous acid one benzene two isodecyl ester 15 parts, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 2 parts.
Embodiment 2
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 45 parts, 20 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 5 parts, 1,4-hexamethylene Diisocyanate 25 parts, 1,5-naphthalene diisocyanate 5 parts, 1,4-butynediols 6 parts, 1,4-bis-(2-hydroxyl second Epoxide) benzene 1 part, 4,4 '-benzidine sulfone 5 parts, dibutyl tin laurate 0.01 part, double dodecyl Ditallowdimethyl ammonium bromide 5 parts, graphene oxide 2 parts, CNT 2 parts, hydroxyl polydimethylsiloxane 12 parts, Heat stabilizer 3 parts, polystyrene 10 parts, rare earth compounding 3 parts；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 15 parts, molybdenum trioxide 2 Part, bismuth oxide 8 parts, 2,2'-ethylenedioxybis(ethanol). be double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] 1 part, Diphosphorous acid tetramethylolmethane two isodecyl ester 8 parts, phosphorous acid one benzene two isodecyl ester 2 parts, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 10 parts.
Embodiment 3
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 60 parts, 12 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 17 parts, 1,4-hexamethylene Alkane diisocyanate 18 parts, 1,5-naphthalene diisocyanate 20 parts, 1,4-butynediols 3.5 parts, 1,4-bis-(2- Hydroxyl-oxethyl) benzene 3.8 parts, 4,4 '-benzidine sulfone 3 parts, dibutyl tin laurate 0.12 part, double Dodecydimethylammonium bronides 3.2 parts, graphene oxide 6.5 parts, CNT 5.8 parts, the poly-diformazan of hydroxyl Radical siloxane 10 parts, heat stabilizer 10 parts, polystyrene 6.5 parts, rare earth compounding 5 parts；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 13 parts, molybdenum trioxide 8 Part, bismuth oxide 6.2 parts, 2,2'-ethylenedioxybis(ethanol). be double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propanoic acid Ester] 5.8 parts, diphosphorous acid tetramethylolmethane two isodecyl ester 6 parts, phosphorous acid one benzene two isodecyl ester 8 parts, 2,2 '- Thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 8.5 parts；
Wherein, described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight 20 parts of polyvinyl alcohol, 2 parts of isopropanolamines are added in 100 parts of acetonitriles by part, are uniformly mixing to obtain molten at 65 DEG C Liquid A；By weight nitroxyl chloride phenyl formate is dissolved in 30 parts of acetonitriles by 3 parts and obtains solution B；At 10 DEG C, Adding in 150 parts of solution A by 35 parts of solution B by weight, then stirring reaction 20h, reaction is put into after terminating In refrigerator, freezing 5h, obtains modified polyvinylalcohol through filtration, evaporation, precipitating, drying；By weight by 50 Part chitosan is dissolved in 100 parts of deionized waters, is cooled to room temperature, is subsequently adding 5 at 55 DEG C after stirring 50min Part modified polyvinylalcohol, stirs 20h at 35 DEG C, stirring terminate after through dialysis, rotary evaporation, be dried to obtain Grafting polyvinyl alcohol；By weight 3 parts of grafting polyvinyl alcohols are added in 100 parts of deionized waters, add 0.2 part Europium chloride, 0.5 part of lanthanum chloride, then the pH value of regulation system is neutral, reacts 30min, instead at 75 DEG C Described rare earth compounding is obtained through dialysing, be dried, grinding after should terminating.
Embodiment 4
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 55 parts, 15 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 11 parts, 1,4-hexamethylene Alkane diisocyanate 21 parts, 1,5-naphthalene diisocyanate 15 parts, 1,4-butynediols 4.2 parts, 1,4-bis-(2- Hydroxyl-oxethyl) benzene 3 parts, 4,4 '-benzidine sulfone 3.8 parts, dibutyl tin laurate 0.05 part, double Dodecydimethylammonium bronides 4 parts, graphene oxide 5.5 parts, CNT 7 parts, hydroxyl poly dimethyl silicon 6 parts of oxygen alkane, heat stabilizer 12.5 parts, polystyrene 5.8 parts, rare earth compounding 7 parts；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 8 parts, molybdenum trioxide 11 Part, bismuth oxide 3.5 parts, 2,2'-ethylenedioxybis(ethanol). be double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] 7 Part, diphosphorous acid tetramethylolmethane two isodecyl ester 4.5 parts, phosphorous acid one benzene two isodecyl ester 10 parts, 2,2 '-sulfur generation Double [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionates] 5.5 parts；
Wherein, described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight 50 parts of polyvinyl alcohol, 0.8 part of isopropanolamine are added in 100 parts of acetonitriles by part, are uniformly mixing to obtain at 75 DEG C Solution A；By weight nitroxyl chloride phenyl formate is dissolved in 50 parts of acetonitriles by 8 parts and obtains solution B；At 5 DEG C, Adding in 120 parts of solution A by 50 parts of solution B by weight, then stirring reaction 15h, reaction is put into after terminating In refrigerator, freezing 10h, obtains modified polyvinylalcohol through filtration, evaporation, precipitating, drying；By weight by 20 Part chitosan is dissolved in 100 parts of deionized waters, is cooled to room temperature, is subsequently adding at 70 DEG C after stirring 30min 12 parts of modified polyvinylalcohols, stir 35h at 30 DEG C, stirring terminate after through dialysis, rotary evaporation, dry To grafting polyvinyl alcohol；By weight 1.5 parts of grafting polyvinyl alcohols are added in 100 parts of deionized waters, add 0.5 part of Europium chloride, 0.1 part of lanthanum chloride, then the pH value of regulation system is neutral, reacts 20min at 85 DEG C, Reaction obtains described rare earth compounding through dialysing, be dried, grinding after terminating.
Embodiment 5
A kind of weather-resistant pu composite that the present invention proposes, its raw material includes by weight: polyoxygenated Propylene glycol 58 parts, 13.5 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 16 parts, 1,4-ring Hexane diisocyanate 20 parts, 1,5-naphthalene diisocyanate 17 parts, 1,4-butynediols 4 parts, 1,4-bis-(2- Hydroxyl-oxethyl) benzene 3.6 parts, 4,4 '-benzidine sulfone 3.2 parts, dibutyl tin laurate 0.1 part, Didodecyldimethylammbromide bromide 3.7 parts, graphene oxide 6 parts, CNT 6.3 parts, the poly-diformazan of hydroxyl Radical siloxane 7.5 parts, heat stabilizer 11 parts, polystyrene 6.2 parts, rare earth compounding 6.5 parts；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 10 parts, molybdenum trioxide 10 parts, bismuth oxide 6 parts, 2,2'-ethylenedioxybis(ethanol). double-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propanoic acid Ester] 6.2 parts, diphosphorous acid tetramethylolmethane two isodecyl ester 5.2 parts, phosphorous acid one benzene two isodecyl ester 8.6 parts, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 7 parts；
Wherein, described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight 35 parts of polyvinyl alcohol, 1.3 parts of isopropanolamines are added in 100 parts of acetonitriles by part, are uniformly mixing to obtain at 70 DEG C Solution A；By weight nitroxyl chloride phenyl formate is dissolved in 42 parts of acetonitriles by 6.5 parts and obtains solution B；At 8 DEG C Under, by weight 43 parts of solution B are added in 140 parts of solution A, then stirring reaction 17.5h, reaction terminates After put in refrigerator freezing 8.5h, obtain modified polyvinylalcohol through filtration, evaporation, precipitating, drying；By weight 35 parts of chitosans are dissolved in 100 parts of deionized waters by amount part, are cooled to room temperature after stirring 40min at 65 DEG C, Be subsequently adding 10 parts of modified polyvinylalcohols, at 33 DEG C stir 28h, stirring terminate after through dialysis, rotary evaporation, It is dried to obtain grafting polyvinyl alcohol；By weight 2.8 parts of grafting polyvinyl alcohols are added in 100 parts of deionized waters, Adding 0.35 part of Europium chloride, 0.35 part of lanthanum chloride, then the pH value of regulation system is neutral, anti-at 80 DEG C Described rare earth compounding is obtained through dialysing, be dried, grinding after answering 26min, reaction to terminate.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention Within the scope of.

Claims (8)

1. a weather-resistant pu composite, it is characterised in that its raw material includes by weight: polyoxy Change propylene glycol 45-65 part, terminal hydroxy liquid silicone rubber 5-20 part, hydroxyl terminated butyl nitrile (HTBN) rubber 5-20 part, 1,4-cyclohexane diisocyanate 10-25 part, 1,5-naphthalene diisocyanate 5-25 part, 1,4-butynediols 2-6 Part, 1,4-bis-(2-hydroxyl-oxethyl) benzene 1-5 part, 4,4 '-benzidine sulfone 2-5 part, tin dilaurate two Butyl tin 0.01-0.15 part, didodecyldimethylammbromide bromide 1-5 part, graphene oxide 2-10 part, carbon Nanotube 2-10 part, hydroxyl polydimethylsiloxane 3-12 part, heat stabilizer 3-15 part, polystyrene 2-10 Part, rare earth compounding 3-8 part；
Wherein, its raw material of described heat stabilizer includes by weight: nano titanium oxide 2-15 part, three oxidations Molybdenum 2-15 part, bismuth oxide 1-8 part, 2,2'-ethylenedioxybis(ethanol). pair-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Propionic ester] 1-10 part, diphosphorous acid tetramethylolmethane two isodecyl ester 1-8 part, phosphorous acid one benzene two isodecyl ester 2-15 Part, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 2-10 part.
Weather-resistant pu composite the most according to claim 1, it is characterised in that in its raw material, Polyoxypropyleneglycol, terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber, 1,4-hexamethylene two are different Cyanate, the weight ratio of 1,5-naphthalene diisocyanate are 50-62:11-18:9-18:15-22:11-22.
Weather-resistant pu composite the most according to claim 1 or claim 2, it is characterised in that its raw material is pressed Weight portion includes: polyoxypropyleneglycol 55-60 part, terminal hydroxy liquid silicone rubber 12-15 part, terminal hydroxy group liquid Body nitrile rubber 11-17 part, 1,4-cyclohexane diisocyanate 18-21 part, 1,5-naphthalene diisocyanate 15-20 Part, 1,4-butynediols 3.5-4.2 part, 1,4-bis-(2-hydroxyl-oxethyl) benzene 3-3.8 part, 4,4 '-diamino Base biphenyl sulfone 3-3.8 part, dibutyl tin laurate 0.05-0.12 part, didodecyldimethylammbromide bromide 3.2-4 part, graphene oxide 5.5-6.5 part, CNT 5.8-7 part, hydroxyl polydimethylsiloxane 6-10 Part, heat stabilizer 10-12.5 part, polystyrene 5.8-6.5 part, rare earth compounding 5-7 part.
4. according to weather-resistant pu composite according to any one of claim 1-3, it is characterised in that Its raw material includes by weight: polyoxypropyleneglycol 58 parts, 13.5 parts of terminal hydroxy liquid silicone rubber, end hydroxyl Base LNBR 16 parts, 1,4-cyclohexane diisocyanate 20 parts, 1,5-naphthalene diisocyanate 17 parts, 1,4-butynediols 4 parts, 1,4-bis-(2-hydroxyl-oxethyl) benzene 3.6 parts, 4,4 '-benzidine sulfone 3.2 Part, dibutyl tin laurate 0.1 part, didodecyldimethylammbromide bromide 3.7 parts, graphene oxide 6 Part, CNT 6.3 parts, hydroxyl polydimethylsiloxane 7.5 parts, heat stabilizer 11 parts, polystyrene 6.2 Part, rare earth compounding 6.5 parts.
5. according to weather-resistant pu composite according to any one of claim 1-4, it is characterised in that Its raw material of described heat stabilizer includes by weight: nano titanium oxide 8-13 part, molybdenum trioxide 8-11 part, Bismuth oxide 3.5-6.2 part, 2,2'-ethylenedioxybis(ethanol). pair-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propanoic acid Ester] 5.8-7 part, diphosphorous acid tetramethylolmethane two isodecyl ester 4.5-6 part, phosphorous acid one benzene two isodecyl ester 8-10 Part, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 5.5-8.5 part.
6. according to weather-resistant pu composite according to any one of claim 1-5, it is characterised in that Its raw material of described heat stabilizer includes by weight: nano titanium oxide 10 parts, molybdenum trioxide 10 parts, three oxygen Change two bismuth 6 parts, 2,2'-ethylenedioxybis(ethanol). pair-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] 6.2 parts, two Asias Phosphoric acid tetramethylolmethane two isodecyl ester 5.2 parts, phosphorous acid one benzene two isodecyl ester 8.6 parts, 2,2 '-thiobis [3-(3,5-di-tert-butyl-hydroxy phenyl) ethyl propionate] 7 parts.
7. according to weather-resistant pu composite according to any one of claim 1-6, it is characterised in that Described rare earth compounding is prepared according to following technique: under the protection of nitrogen, by weight by 20-50 Part polyvinyl alcohol, 0.8-2 part isopropanolamine add in 100 parts of acetonitriles, are uniformly mixing to obtain molten at 65-75 DEG C Liquid A；By weight nitroxyl chloride phenyl formate is dissolved in 30-50 part acetonitrile by 3-8 part and obtains solution B；At 5-10 DEG C Under, by weight 35-50 part solution B is added in 120-150 part solution A, then stirring reaction 15-20h, Freezing 5-10h in refrigerator is put in reaction after terminating, obtain modified poly ethylene through filtration, evaporation, precipitating, drying Alcohol；By weight 20-50 part chitosan is dissolved in 100 parts of deionized waters, stirs at 55-70 DEG C It is cooled to room temperature after 30-50min, is subsequently adding 5-12 part modified polyvinylalcohol, stir at 30-35 DEG C 20-35h, stirring terminate after through dialysis, rotary evaporation, be dried to obtain grafting polyvinyl alcohol；By weight will 1.5-3 part grafting polyvinyl alcohol adds in 100 parts of deionized waters, add 0.2-0.5 part Europium chloride, 0.1-0.5 Part lanthanum chloride, then the pH value of regulation system is neutral, reacts 20-30min at 75-85 DEG C, and reaction terminates Described rare earth compounding is obtained by dialysing, be dried, grinding.
8. according to weather-resistant pu composite according to any one of claim 1-7, it is characterised in that Described rare earth compounding is prepared according to following technique: under the protection of nitrogen, gathers 35 parts by weight Vinyl alcohol, 1.3 parts of isopropanolamines add in 100 parts of acetonitriles, are uniformly mixing to obtain solution A at 70 DEG C；By weight Nitroxyl chloride phenyl formate is dissolved in 42 parts of acetonitriles and obtains solution B by amount part by 6.5 parts；At 8 DEG C, by weight 43 parts of solution B being added in 140 parts of solution A, then stirring reaction 17.5h, reaction is put in refrigerator after terminating Freezing 8.5h, obtains modified polyvinylalcohol through filtration, evaporation, precipitating, drying；By weight by 35 parts of shells Polysaccharide is dissolved in 100 parts of deionized waters, is cooled to room temperature, is subsequently adding 10 parts at 65 DEG C after stirring 40min Modified polyvinylalcohol, stirs 28h at 33 DEG C, stirring terminate after through dialysis, rotary evaporation, be dried to obtain and connect Branch polyvinyl alcohol；By weight 2.8 parts of grafting polyvinyl alcohols are added in 100 parts of deionized waters, add 0.35 Part Europium chloride, 0.35 part of lanthanum chloride, then the pH value of regulation system is neutral, reacts 26min at 80 DEG C, Reaction obtains described rare earth compounding through dialysing, be dried, grinding after terminating.
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Application publication date: 20160803