CN104844778B - The dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide and preparation and application - Google Patents

The dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide and preparation and application Download PDF

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CN104844778B
CN104844778B CN201510223444.6A CN201510223444A CN104844778B CN 104844778 B CN104844778 B CN 104844778B CN 201510223444 A CN201510223444 A CN 201510223444A CN 104844778 B CN104844778 B CN 104844778B
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needle
zinc oxide
aqueous polyurethane
aminopropyl
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CN104844778A (en
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刘伟区
夏侯国论
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Guangzhou Chemical Co Ltd of CAS
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Abstract

The present invention discloses the dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide and preparation and application.The dispersion includes following components：1~8 mass parts γ aminopropyl triethoxysilanes are modified four-needle-like zinc oxide, 100 mass parts PEPAs, 13~91 mass parts diisocyanate, 10~25 mass parts amido silicon oils, 0~0.5 mass parts organo-metallic catalyst, 8~16 mass parts multi-hydroxy carboxy acids, 0.3~10 mass parts crosslinking agent, 6.2~18 mass parts nertralizers, 1~8 mass parts chain extender, 0.2~2.0 mass parts defoamer.The amino that four-needle-like zinc oxide surface is modified in γ aminopropyl triethoxysilanes can be connected in polyurethane molecular chain by chemical reaction, is improved compatibility, is advantageous to the dispersed of four-needle-like zinc oxide.Dispersion produced by the present invention has good thermal property, mechanical property, water resistance and antistatic behaviour, anti-ultraviolet ageing ability.

Description

The dual modified polyester-type aqueous polyurethane point of a kind of organosilicon and four-needle-like zinc oxide Granular media and preparation and application
Technical field
The invention belongs to chemical field, is related to a kind of synthesis of polyester-type aqueous polyurethane dispersion, and in particular to The dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide and preparation method and application.
Background technology
Aqueous polyurethane (WPU) be using water replace organic solvent as decentralized medium polyurethane system, because its is nontoxic, no Combustion and free of contamination characteristic just progressively substitute conventional solvent type polyurethane, turn into the important directions of polyurethane industrial development.It is water-based Polyurethane can be widely applied to coating, adhesive, fabric coating and finishing agent, paper and fiber strength agent, leather finish Agent.However, often there is resistance to acids and bases, heat endurance, ultraviolet-resistant aging and mechanical performance in single aqueous polyurethane The shortcomings of poor.Aqueous polyurethane is divided into polyester-type and the class of polyester-type two, and the wherein water resistance of polyester-type aqueous polyurethane is badly in need of carrying It is high.
Organosilicon material is due to itself having heatproof, weather-proof, electrical insulation capability, low surface tension, low-surface-energy and life The special performances such as inertia are managed, modified polyurethane are often used to, to improve its heat resistance, water resistance, weatherability etc..But due to having The compatibility of machine silicon and polyurethane is bad, therefore can usually reduce the mechanical property of material.
Four acicular type zinc oxide crystal whisker (T-ZnOw) is found the 1940s, is uniquely had in current whisker family The whisker of regular three-D space structure.Four acicular type zinc oxide crystal whisker is a kind of fabulous reinforcing agent, and it is preferable can to assign composite Mechanical property；Moreover, because of its semiconductive, inhaling imparted and highly dense property, can have prepared composite preferable Antistatic behaviour, ageing resistance and damping property.Though four-needle-like zinc oxide can improve the multiple performance of polyurethane, inorganic particulate It is bad with the compatibility of polyurethane, it is difficult to realize and disperse well, therefore its modified effect to polyurethane can be reduced.
Using organosilicon and the common modified aqueous polyurethane of four-needle-like zinc oxide, can assign the more preferable heat resistance of polyurethane, Surface property, mechanical performance and weatherability, so as to expand its application.
The content of the invention
The shortcomings that in order to overcome prior art, is to provide a kind of organosilicon and four pins with deficiency, primary and foremost purpose of the invention The dual modified polyester-type aqueous polyurethane dispersion of shape zinc oxide.
It is water-based another object of the present invention is to provide the dual modified polyester-type of above-mentioned organosilicon and four-needle-like zinc oxide The preparation method of dispersions of polyurethanes.
It is still another object of the present invention to provide the dual modified polyester-type of above-mentioned organosilicon and four-needle-like zinc oxide is water-based The application of dispersions of polyurethanes.
The purpose of the present invention is achieved through the following technical solutions：
The dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide, comprising with the following group Point：1~8 mass parts gamma-aminopropyl-triethoxy-silane is modified four-needle-like zinc oxide, 100 mass parts PEPAs, 13~91 Mass parts diisocyanate, 10~25 mass parts amido silicon oils, 0~0.5 mass parts organo-metallic catalyst, 8~16 mass parts Multi-hydroxy carboxy acid, 0.3~10 mass parts crosslinking agent, 6.2~18 mass parts nertralizers, 1~8 mass parts chain extender, 0.2~2.0 Mass parts defoamer.
Described diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), diphenyl methane -4,4'- diisocyanate (MDI), IPDI (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), XDI (XDI), 1,4- cyclohexane diisocyanates (CHDI) and naphthalene -1,5- diisocyanate (NDI) In one kind.Wherein, preferable diisocyanate is toluene di-isocyanate(TDI) (TDI) or the isocyanic acid of diphenyl methane -4,4'- bis- Ester (MDI).
Described PEPA is selected from average functionality more than 2 and mean molecule quantity is 400~6000 adipic acid system PEPA, pimelic acid system PEPA, suberic acid system PEPA, glutaric acid system PEPA, decanedioic acid system PEPA, oxalic acid series PEPA, Succinic Acid Polyester Polyols PEPA, polycaprolactone polyol, polycarbonate polyol Alcohol, cis-butenedioic anhydride PEPA, benzoic anhydride polyester polyol, to one kind in benzene PEPA and random copolymerization ester polyol.Its In, PEPA is preferably adipic acid system PEPA or polycaprolactone polyol.
Described amido silicon oil be selected from mean molecule quantity be 3000~10000 double ended type amino polydimethyl siloxane and One kind in the type amino polydimethyl siloxane of side.
Described organo-metallic catalyst is being selected from stannous octoate, dibutyl tin dilaurate, lead octoate and two acetic acid two just One kind in butyl tin；Wherein, organo-metallic catalyst is preferably dibutyl tin dilaurate.
The one kind of described multi-hydroxy carboxy acid in dihydromethyl propionic acid, dimethylolpropionic acid and tartaric acid.
Described crosslinking agent is selected from trimethylolpropane.
Described nertralizer is in triethylamine, trimethylamine, N, N- dimethylethanolamines, diethanol amine and triethanolamine It is a kind of.
Described chain extender is selected from 1,4- butanediols, ethylene glycol, propane diols, hexylene glycol, cyclohexanediol, terephthalic acid (TPA) two At least one of hydroxyl ethyl ester and trimethyolol propane monoallyl ether；More preferably 1,4- butanediols.
Described defoamer is selected from organic silicon defoamer, mineral oil defoaming agent and polar organic compounds class defoamer In one kind.More preferably organic silicon defoamer.
Described gamma-aminopropyl-triethoxy-silane is modified the preparation method of four-needle-like zinc oxide, comprises the steps of：
(1) by 12~14 mass parts absolute ethyl alcohols, 2~4 mass parts deionized waters and 4 mass parts γ-ethoxy of aminopropyl three Base silane mixes, and hydrolyzes 0.5~1 hour at room temperature, obtains gamma-aminopropyl-triethoxy-silane mixed liquor；
(2) 25 mass parts four-needle-like zinc oxides are mixed with 150~300 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5~1 Hour, obtain the alcohol dispersion liquid of four-needle-like zinc oxide；
(3) add gamma-aminopropyl-triethoxy-silane mixed liquor made from 5~20 mass parts steps (1) to 175~ In the alcohol dispersion liquid of four-needle-like zinc oxide made from 350 mass parts steps (2), the return stirring 1.5 in 60~80 DEG C of oil baths ~3 hours；Reaction filters after terminating, and is washed 3~5 times with absolute ethyl alcohol, is dried in vacuo 24~48 hours at 60~70 DEG C, i.e., Obtain gamma-aminopropyl-triethoxy-silane and be modified four-needle-like zinc oxide.
The preparation method of the dual modified polyester-type aqueous polyurethane dispersion of described organosilicon and four-needle-like zinc oxide, Comprise the following steps：
1~8 mass parts gamma-aminopropyl-triethoxy-silane is taken to be modified four-needle-like zinc oxide, the isocyanide of 13~91 mass parts two Acid esters, 100 mass parts PEPAs, 10~25 mass parts amido silicon oils, under nitrogen protection, in -10~0 DEG C of stirring reaction 0.5~1 hour, 0~0.5 mass parts organo-metallic catalyst is then added, is warming up to 50~90 DEG C of stirring reactions 2~3 hours, 8~16 mass parts multi-hydroxy carboxy acids and 0.3~10 mass parts crosslinking agent are added, continue reaction 2~4 hours, with acetone viscosity reduction, Obtain prepolymer.Room temperature is then cooled to, 6.2~18 mass parts nertralizers is added and neutralizes into salt, add water to be stirred vigorously emulsification.Breast 1~8 mass parts chain extender, 0.2~2.0 mass parts defoamer are added after change, stirs 20~60 minutes at 20~60 DEG C, finally The acetone in removing system is evaporated under reduced pressure, polyester-type aqueous polyurethane dispersion is made.Then it is cast the template in horizontal On, film forming is spontaneously dried at room temperature, after being then dried under vacuum to permanent quality, carries out performance test.
Described diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), diphenyl methane -4,4'- diisocyanate (MDI), IPDI (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), XDI (XDI), 1,4- cyclohexane diisocyanates (CHDI) and naphthalene -1,5- diisocyanate (NDI) In one kind.Wherein, preferable diisocyanate is toluene di-isocyanate(TDI) (TDI) or the isocyanic acid of diphenyl methane -4,4'- bis- Ester (MDI).
Described PEPA is selected from average functionality more than 2 and mean molecule quantity is 400~6000 adipic acid system PEPA, pimelic acid system PEPA, suberic acid system PEPA, glutaric acid system PEPA, decanedioic acid system PEPA, oxalic acid series PEPA, Succinic Acid Polyester Polyols PEPA, polycaprolactone polyol, polycarbonate polyol Alcohol, cis-butenedioic anhydride PEPA, benzoic anhydride polyester polyol, at least one in benzene PEPA and random copolymerization ester polyol Kind.Wherein, PEPA is preferably adipic acid system PEPA or polycaprolactone polyol.
Described amido silicon oil be selected from mean molecule quantity be 3000~10000 double ended type amino polydimethyl siloxane and One kind in the type amino polydimethyl siloxane of side.
Described organo-metallic catalyst is being selected from stannous octoate, dibutyl tin dilaurate, lead octoate and two acetic acid two just One kind in butyl tin；Wherein, organo-metallic catalyst is preferably dibutyl tin dilaurate.
The one kind of described multi-hydroxy carboxy acid in dihydromethyl propionic acid, dimethylolpropionic acid and tartaric acid.
Described crosslinking agent is selected from trimethylolpropane.
Described nertralizer is in triethylamine, trimethylamine, N, N- dimethylethanolamines, diethanol amine and triethanolamine It is a kind of.
Described chain extender is selected from 1,4- butanediols, ethylene glycol, propane diols, hexylene glycol, cyclohexanediol, terephthalic acid (TPA) two At least one of hydroxyl ethyl ester and trimethyolol propane monoallyl ether；More preferably 1,4- butanediols.
Described defoamer is selected from organic silicon defoamer, mineral oil defoaming agent and polar organic compounds class defoamer In one kind.More preferably organic silicon defoamer.
Described gamma-aminopropyl-triethoxy-silane is modified the preparation method of four-needle-like zinc oxide, comprises the steps of：
(1) by 12~14 mass parts absolute ethyl alcohols, 2~4 mass parts deionized waters and 4 mass parts γ-ethoxy of aminopropyl three Base silane mixes, and hydrolyzes 0.5~1 hour at room temperature, obtains gamma-aminopropyl-triethoxy-silane mixed liquor；
(2) 25 mass parts four-needle-like zinc oxides are mixed with 150~300 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5~1 Hour, obtain the alcohol dispersion liquid of four-needle-like zinc oxide；
(3) add gamma-aminopropyl-triethoxy-silane mixed liquor made from 5~20 mass parts steps (1) to 175~ In the alcohol dispersion liquid of four-needle-like zinc oxide made from 350 mass parts steps (2), the return stirring 1.5 in 60~80 DEG C of oil baths ~3 hours；Reaction filters after terminating, and is washed 3~5 times with absolute ethyl alcohol, is dried in vacuo 24~48 hours at 60~70 DEG C, i.e., Obtain gamma-aminopropyl-triethoxy-silane and be modified four-needle-like zinc oxide.
The dual modified polyester-type aqueous polyurethane dispersion of described organosilicon and four-needle-like zinc oxide can be applied to wood Device coating, electrocoating paint, building coating, paper process coating, glass fiber coating, electrophoretic paint etc..
The present invention is had the following advantages and effect relative to prior art：
(1) the polyester-type aqueous polyurethane that the organosilicon and four-needle-like zinc oxide prepared in the present invention is modified jointly disperses Body, make not only with good thermal property, mechanical property, water resistance but also with antistatic behaviour, anti-ultraviolet ageing ability.
(2) present invention is modified using gamma-aminopropyl-triethoxy-silane to four-needle-like zinc oxide, aoxidizes four needle-likes Zinc surface is connected to a large amount of silane couplers, increases the compatibility of four-needle-like zinc oxide and polyurethane.In addition, γ-aminopropyl For triethoxysilane coupling agent during modified four-needle-like zinc oxide, its amino has neither part nor lot in reaction.The amino remained can It is connected to by chemical reaction in polyurethane molecular chain, which further improves the compatible of four-needle-like zinc oxide and polyurethane matrix Property.
(3) present invention adds four-needle-like zinc oxide, four-needle-like zinc oxide than common organic silicon modified polyurethane system Pin can prevent the aggregation of organosilicon to a certain extent, so as to reduce the phase separation journey between organosilicon and polyurethane Degree, and then improve the overall performance of material.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Each performance test methods are as follows in following examples：
TG is using the resistance to ftir Analysis combination analysis instrument of TG209F3- Brookers TENSOR 27 test of speeding of Germany, N2Atmosphere, 10 DEG C/min of heating rate.
The measure of water resistance uses infusion method, that is, weighs a certain amount of glued membrane (W1), it is immersed in 25 DEG C or so distilled water, Taken out after 24h, quickly wipe surface moisture with filter paper, weigh (W immediately2), water absorption rate (P) is calculated by equation below：P= [(W2-W1)/W1] × 100%.
Elongation at break and tensile strength newly think carefully material tests Co., Ltd CMT4503 electronic tensile machines using Shenzhen, According to the standard testings of GB/T 13022-1991.
Ultraviolet ageing uses the permanent company BHO-401A ageing ovens in Shanghai one, and ageing time is 168 hours.
Embodiment 1
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 12 mass parts absolute ethyl alcohols, 4 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 0.5 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 150 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5 hour, obtains four The alcohol dispersion liquid of acicular type zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 5 mass parts steps (1) is added to 175 mass parts and walked Suddenly in the alcohol dispersion liquid of four-needle-like zinc oxide made from (2), return stirring 1.5 hours in 70 DEG C of oil baths.After reaction terminates Filter, washed 3 times with absolute ethyl alcohol, be dried in vacuo 48 hours at 60 DEG C, produce gamma-aminopropyl-triethoxy-silane and be modified four Acicular type zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
1g gamma-aminopropyl-triethoxy-silanes are modified four-needle-like zinc oxide and 18g toluene di-isocyanate(TDI)s, 100g are average Molecular weight is 2000, the α that polycaprolactone diols that hydroxyl value is 55-58,10g molecular weight are 5000, ω-two aminopropyls end-blocking Dimethyl silicone polymer, under nitrogen protection, in -10 DEG C of stirring reactions 1 hour, 0.5g stannous octoates are then added, are warming up to 70 DEG C of stirring reactions 2 hours, add 8g dihydromethyl propionic acids and 1g trimethylolpropanes, continue reaction 4 hours, are dropped with acetone It is viscous, obtain prepolymer.Room temperature is then cooled to, 6.2g triethylamines is added and neutralizes into salt, add water to be stirred vigorously emulsification.Add after emulsification Enter 3g BDOs and 0.2g organic silicon defoamers, stir at 50 DEG C 40 minutes, be finally evaporated under reduced pressure in removing system Acetone, polyester-type aqueous polyurethane dispersion is made.Then it is cast in the template of horizontal, is spontaneously dried at room temperature Film, after being then dried under vacuum to permanent quality, carry out performance test.
Its maximum heat weightless temperature is measured as 368.5 DEG C, water absorption rate 6.5%, elongation at break 380%, stretching is by force Spend for 16MPa.After ultraviolet ageing, its elongation at break is 361%, tensile strength 13.8MPa.
Embodiment 2
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 14 mass parts absolute ethyl alcohols, 2 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 1 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 300 mass parts absolute ethyl alcohols, ultrasonic disperse 1 hour, obtains four pins The alcohol dispersion liquid of shape zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 20 mass parts steps (1) is added to 325 mass parts In the alcohol dispersion liquid of four-needle-like zinc oxide made from step (2), return stirring 3 hours in 60 DEG C of oil baths.After reaction terminates Filter, washed 5 times with absolute ethyl alcohol, be dried in vacuo 24 hours at 70 DEG C, produce gamma-aminopropyl-triethoxy-silane and be modified four Acicular type zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
2.5g gamma-aminopropyl-triethoxy-silanes are modified four-needle-like zinc oxide, the isocyanide of 29g diphenyl methanes -4,4 '-two Acid esters, 100g mean molecule quantities are 3000, and hydroxyl value is 50-55 polyadipate ethylene glycol trihydroxymethylpropanyl ester polyalcohol, 25g Molecular weight is 6000 aminoethylaminopropyl dimethyl silicone polymer, under nitrogen protection, in 0 DEG C of stirring reaction 0.5 hour, so Add 0.05g dibutyl tin dilaurates afterwards, be warming up to 80 DEG C of stirring reactions 1 hour, add 16g dimethylolpropionic acids and 10g trimethylolpropanes, continue reaction 3 hours, with acetone viscosity reduction, obtain prepolymer.Room temperature is then cooled to, adds 6.4g tri- Methylamine is neutralized into salt, adds water to be stirred vigorously emulsification.2g ethylene glycol and 0.8g organic silicon defoamers are added after emulsification, at 20 DEG C Stirring 60 minutes, the acetone in removing system is finally evaporated under reduced pressure, polyester-type aqueous polyurethane dispersion is made.Then flowed Prolong in the template of horizontal, spontaneously dry film forming at room temperature, after being then dried under vacuum to permanent quality, carry out performance test.
Its maximum heat weightless temperature is measured as 385.2 DEG C, water absorption rate 7.3%, elongation at break 295%, stretching is by force Spend for 23.4MPa.After ultraviolet ageing, its elongation at break is 278%, tensile strength 19.6MPa.
Embodiment 3
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 13 mass parts absolute ethyl alcohols, 3 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 0.8 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 220 mass parts absolute ethyl alcohols, ultrasonic disperse 0.7 hour, obtains four The alcohol dispersion liquid of acicular type zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 18 mass parts steps (1) is added to 245 mass parts In the alcohol dispersion liquid of four-needle-like zinc oxide made from step (2), return stirring 2 hours in 80 DEG C of oil baths.After reaction terminates Filter, washed 4 times with absolute ethyl alcohol, be dried in vacuo 36 hours at 65 DEG C, produce gamma-aminopropyl-triethoxy-silane and be modified four Acicular type zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
4g gamma-aminopropyl-triethoxy-silanes are modified four-needle-like zinc oxide, 91g IPDIs, 100g Mean molecule quantity is 500, the α that PCDL that hydroxyl value is 220-230,20g molecular weight are 10000, ω-two aminopropyls The dimethyl silicone polymer of end-blocking, under nitrogen protection, in -10 DEG C of stirring reactions 0.5 hour, 0.3g lead octoates are then added, It is warming up to 50 DEG C of stirring reactions 1 hour, adds 16g tartaric acid and 0.5g trimethylolpropanes, continues reaction 2 hours, with third Ketone viscosity reduction, obtains prepolymer.Room temperature is then cooled to, 18g N, N- dimethylethanolamine is added and neutralizes into salt, add water acutely to stir Mix emulsification.2g propane diols and 1.0g mineral oil defoaming agents are added after emulsification, stirs 30 minutes at 30 DEG C, is finally evaporated under reduced pressure Acetone in removing system, polyester-type aqueous polyurethane dispersion is made.Then it is cast in the template of horizontal, at room temperature Film forming is spontaneously dried, after being then dried under vacuum to permanent quality, carries out performance test.
Its maximum heat weightless temperature is measured as 392.1 DEG C, water absorption rate 5.8%, elongation at break 201%, stretching is by force Spend for 28.4MPa.After ultraviolet ageing, its elongation at break is 164%, tensile strength 25.6MPa.
Embodiment 4
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 12 mass parts absolute ethyl alcohols, 4 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 0.5 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 200 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5 hour, obtains four The alcohol dispersion liquid of acicular type zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 15 mass parts steps (1) is added to 225 mass parts In the alcohol dispersion liquid of four-needle-like zinc oxide made from step (2), return stirring 2.5 hours in 80 DEG C of oil baths.Reaction terminates After filter, washed 4 times with absolute ethyl alcohol, be dried in vacuo 40 hours at 65 DEG C, produce gamma-aminopropyl-triethoxy-silane modification Four-needle-like zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
8g gamma-aminopropyl-triethoxy-silanes are modified four-needle-like zinc oxide, 13g IPDIs, 100g Mean molecule quantity is 6000, the ammonia that poly- suberic acid diglycol esterdiol, the 18g molecular weight that hydroxyl value is 16-20 are 3000 Ethylaminopropyl dimethyl silicone polymer, under nitrogen protection, in -5 DEG C of stirring reactions 0.7 hour, then add the vinegar of 0.4g bis- Sour di-n-butyl tin, is warming up to 80 DEG C of stirring reactions 1 hour, adds 12g dihydromethyl propionic acids and 0.3g trimethylolpropanes, after Continuous reaction 3 hours, with acetone viscosity reduction, obtains prepolymer.Room temperature is then cooled to, 9.5g diethanol amine is added and neutralizes into salt, add Water is stirred vigorously emulsification.1g hexylene glycols and 1.4g mineral oil defoaming agents are added after emulsification, stirs 50 minutes at 60 DEG C, finally The acetone in removing system is evaporated under reduced pressure, polyester-type aqueous polyurethane dispersion is made.Then it is cast the template in horizontal On, film forming is spontaneously dried at room temperature, after being then dried under vacuum to permanent quality, carries out performance test.
Its maximum heat weightless temperature is measured as 372.8 DEG C, water absorption rate 7.1%, elongation at break 352%, stretching is by force Spend for 17.9MPa, after ultraviolet ageing, its elongation at break is 248%, tensile strength 15.4MPa.
Embodiment 5
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 12 mass parts absolute ethyl alcohols, 4 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 0.5 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 200 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5 hour, obtains four The alcohol dispersion liquid of acicular type zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 8 mass parts steps (1) is added to 225 mass parts and walked Suddenly in the alcohol dispersion liquid of four-needle-like zinc oxide made from (2), return stirring 2 hours in 80 DEG C of oil baths.Reaction is taken out after terminating Filter, is washed 3 times with absolute ethyl alcohol, is dried in vacuo 30 hours at 65 DEG C, is produced gamma-aminopropyl-triethoxy-silane and is modified four pins Shape zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
3g gamma-aminopropyl-triethoxy-silanes modification four-needle-like zinc oxide is put down with 83g PPDIs and 100g Average molecular weight is 400, the α, ω-diamino that polydiethylene glycol sebacate glycol that hydroxyl value is 275-285,12g molecular weight are 4000 The dimethyl silicone polymer of propyl group end-blocking, under nitrogen protection, in -10 DEG C of stirring reactions 0.5 hour, then heat to 50 DEG C and stir Reaction 1 hour is mixed, adds 12g dihydromethyl propionic acids and 1.5g trimethylolpropanes, continues reaction 3 hours, with acetone viscosity reduction, obtains To prepolymer.Room temperature is then cooled to, 13.3g triethanolamines is added and neutralizes into salt, add water to be stirred vigorously emulsification.Added after emulsification 2g cyclohexanediols, the hydroxyl ethyl ester of 2g terephthalic acid (TPA)s two and 1.7g polar organic compounds class defoamers, 50 points are stirred at 60 DEG C Clock, the acetone in removing system is finally evaporated under reduced pressure, polyester-type aqueous polyurethane dispersion is made.Then it is cast in horizontal Template on, spontaneously dry film forming at room temperature, after being then dried under vacuum to permanent quality, carry out performance test.
Its maximum heat weightless temperature is measured as 393.8 DEG C, water absorption rate 8.6%, elongation at break 240%, stretching is by force Spend for 25.7MPa.After ultraviolet ageing, its elongation at break is 185%, tensile strength 23.3MPa.
Embodiment 6
First, gamma-aminopropyl-triethoxy-silane is modified the preparation of four-needle-like zinc oxide
(1) 12 mass parts absolute ethyl alcohols, 4 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy-silanes are mixed Close, hydrolyze 0.5 hour at room temperature, obtain gamma-aminopropyl-triethoxy-silane mixed liquor.
(2) 25 mass parts four-needle-like zinc oxides are mixed with 200 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5 hour, obtains four The alcohol dispersion liquid of acicular type zinc oxide.
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 10 mass parts steps (1) is added to 225 mass parts In the alcohol dispersion liquid of four-needle-like zinc oxide made from step (2), return stirring 2 hours in 80 DEG C of oil baths.After reaction terminates Filter, washed 3 times with absolute ethyl alcohol, be dried in vacuo 24 hours at 65 DEG C, produce gamma-aminopropyl-triethoxy-silane and be modified four Acicular type zinc oxide.
2nd, the preparation of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide
1.5g gamma-aminopropyl-triethoxy-silanes are modified into four-needle-like zinc oxide, 36g toluene di-isocyanate(TDI)s, 100g to put down Average molecular weight is 1000, hydroxyl value be 110-115 to benzene polyester diol, 10g molecular weight is 8000 α, ω-two aminopropyls envelope The dimethyl silicone polymer at end, under nitrogen protection, in -5 DEG C of stirring reactions 1 hour, then add 0.4g dibutyl tins osmanthus Sour tin, is warming up to 70 DEG C of stirring reactions 1 hour, adds 13g dihydromethyl propionic acids and 2.5g trimethylolpropanes, continues reaction 2 Hour, with acetone viscosity reduction, obtain prepolymer.Room temperature is then cooled to, 9.8g triethylamines is added and neutralizes into salt, add water to be stirred vigorously Emulsification.8g trimethyolol propane monoallyl ethers and 2.0g polar organic compounds class defoamers are added after emulsification, at 30 DEG C Stirring 25 minutes, the acetone in removing system is finally evaporated under reduced pressure, polyester-type aqueous polyurethane dispersion is made.Then flowed Prolong in the template of horizontal, spontaneously dry film forming at room temperature, after being then dried under vacuum to permanent quality, carry out performance test.
Its maximum heat weightless temperature is measured as 385.4 DEG C, water absorption rate 7.1%, elongation at break 366%, stretching is by force Spend for 24.1MPa, after ultraviolet ageing, its elongation at break is 354%, tensile strength 21.3MPa.
Comparative example 1
Table 1
Wherein, sample A is pure polyester-type aqueous polyurethane in table 1, and its preparation method is：By 18g toluene di-isocyanate(TDI)s, 100g mean molecule quantities be 2000, hydroxyl value be 55-58 polycaprolactone diols, 0.5g stannous octoates, under nitrogen protection, 70 DEG C of stirring reactions 2 hours, 8g dihydromethyl propionic acids and 1g trimethylolpropanes are then added, continue reaction 4 hours, use acetone Viscosity reduction, obtain prepolymer.Room temperature is then cooled to, 6.2g triethylamines is added and neutralizes into salt, add water to be stirred vigorously emulsification.After emulsification 3g BDOs and 0.2g organic silicon defoamers are added, is stirred at 50 DEG C 40 minutes, removing system is finally evaporated under reduced pressure In acetone, polyester-type aqueous polyurethane dispersion is made.Then it is cast in the template of horizontal, is spontaneously dried at room temperature Film forming, after being then dried under vacuum to permanent quality, carry out performance test.
It can be seen from Table 1 that compared with unmodified pure polyurethane (sample A), organosilicon and four made from embodiment 1 The maximum heat weightless temperature of the dual modified polyester-type aqueous polyurethane dispersion of acicular type zinc oxide significantly increases, water absorption rate is notable Reduce, tensile strength improves.After ultraviolet ageing, the tensile strength and elongation at break of two kinds of samples all reduce, still The reduction degree of embodiment 1 is less than sample A.This comparative example illustrates organosilicon and four-needle-like zinc oxide pair prepared by the present invention Modified polyester-type aqueous polyurethane dispersion has good thermal property, water resistance, mechanical property and uvioresistant energy again Power.
Comparative example 2
Table 2
Wherein, sample B is pure polyester-type aqueous polyurethane in table 2, and its preparation method is：By 29g diphenyl methane -4, 4 '-diisocyanate, 100g mean molecule quantities are 3000, and hydroxyl value is 50-55 polyadipate ethylene glycol trihydroxymethylpropanyl ester Polyalcohol, 0.05g dibutyl tin dilaurates, under nitrogen protection, in 80 DEG C of stirring reactions 1 hour, then add 16g dihydroxies Methylbutanoic acid and 10g trimethylolpropanes, continue reaction 3 hours, with acetone viscosity reduction, obtain prepolymer.It is then cooled to room temperature, Add 6.4g trimethylamines to neutralize into salt, add water to be stirred vigorously emulsification.2g ethylene glycol and the defoaming of 0.8g organic silicons are added after emulsification Agent, stirred at 20 DEG C 60 minutes, the acetone in removing system is finally evaporated under reduced pressure, polyester-type aqueous polyurethane is made and disperses Body.Then it is cast in the template of horizontal, spontaneously dries film forming at room temperature, after being then dried under vacuum to permanent quality, is carried out Performance test.
It can be seen from Table 2 that compared with unmodified pure polyurethane (sample B), organosilicon and four made from embodiment 2 The maximum heat weightless temperature of the dual modified polyester-type aqueous polyurethane dispersion of acicular type zinc oxide significantly increases, water absorption rate is notable Reduce, tensile strength improves.After ultraviolet ageing, the tensile strength and elongation at break of two kinds of samples all reduce, still The reduction degree of embodiment 2 is less than sample B.This comparative example illustrates organosilicon and four-needle-like zinc oxide pair prepared by the present invention Modified polyester-type aqueous polyurethane dispersion has good thermal property, water resistance, mechanical property and uvioresistant energy again Power.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (9)

1. a kind of organosilicon and the dual modified polyester-type aqueous polyurethane dispersion of four-needle-like zinc oxide, it is characterised in that include Following components：1~8 mass parts gamma-aminopropyl-triethoxy-silane be modified four-needle-like zinc oxide, 100 mass parts PEPAs, 13~91 mass parts diisocyanate, 10~25 mass parts amido silicon oils, 0~0.5 mass parts organo-metallic catalyst, 8~16 Mass parts multi-hydroxy carboxy acid, 0.3~10 mass parts crosslinking agent, 6.2~18 mass parts nertralizers, 1~8 mass parts chain extender, 0.2 ~2.0 mass parts defoamers；
Described gamma-aminopropyl-triethoxy-silane is modified the preparation method of four-needle-like zinc oxide, comprises the steps of：
(1) by 12~14 mass parts absolute ethyl alcohols, 2~4 mass parts deionized waters and 4 mass parts gamma-aminopropyl-triethoxy silicon Alkane mixes, and hydrolyzes 0.5~1 hour at room temperature, obtains gamma-aminopropyl-triethoxy-silane mixed liquor；
(2) 25 mass parts four-needle-like zinc oxides are mixed with 150~300 mass parts absolute ethyl alcohols, ultrasonic disperse 0.5~1 hour, Obtain the alcohol dispersion liquid of four-needle-like zinc oxide；
(3) gamma-aminopropyl-triethoxy-silane mixed liquor made from 5~20 mass parts steps (1) is added to 175~350 matter Measure in the alcohol dispersion liquid of four-needle-like zinc oxide made from part step (2), return stirring 1.5~3 is small in 60~80 DEG C of oil baths When；Reaction terminate after filter, washed 3~5 times with absolute ethyl alcohol, be dried in vacuo 24~48 hours at 60~70 DEG C, produce γ- Aminopropyl triethoxysilane is modified four-needle-like zinc oxide；
The preparation method of the dual modified polyester-type aqueous polyurethane dispersion of described organosilicon and four-needle-like zinc oxide, including Following steps：
Take 1~8 mass parts gamma-aminopropyl-triethoxy-silane be modified four-needle-like zinc oxide, 13~91 mass parts diisocyanate, 100 mass parts PEPAs, 10~25 mass parts amido silicon oils, under nitrogen protection, -10~0 DEG C of stirring reaction 0.5~ 1 hour, 0~0.5 mass parts organo-metallic catalyst is then added, is warming up to 50~90 DEG C of stirring reactions 1~2 hour, then is added Enter 8~16 mass parts multi-hydroxy carboxy acids and 0.3~10 mass parts crosslinking agent, continue reaction 2~4 hours, with acetone viscosity reduction, obtain Prepolymer；Room temperature is then cooled to, 6.2~18 mass parts nertralizers is added and neutralizes into salt, add water to be stirred vigorously emulsification；After emulsification 1~8 mass parts chain extender, 0.2~2.0 mass parts defoamer are added, stirs 20~60 minutes at 20~60 DEG C, finally depressurizes The acetone in removing system is evaporated, polyester-type aqueous polyurethane dispersion is made.
2. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described diisocyanate is that toluene di-isocyanate(TDI), diphenyl methane -4,4'- diisocyanate, isophorone two are different Cyanate, hexamethylene diisocyanate, PPDI, XDI, 1,4- hexamethylenes two are different One kind in cyanate and naphthalene -1,5- diisocyanate.
3. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described PEPA be average functionality be more than 2 and mean molecule quantity be 400~6000 adipic acid system polyester it is more First alcohol, pimelic acid system PEPA, suberic acid system PEPA, glutaric acid system PEPA, decanedioic acid system polyester are more First alcohol, oxalic acid series PEPA, Succinic Acid Polyester Polyols PEPA, polycaprolactone polyol, polycarbonate polyol, cis-butenedioic anhydride PEPA, benzoic anhydride polyester polyol, at least one of benzene PEPA and random copolymerization ester polyol.
4. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described amido silicon oil is the double ended type amino polydimethyl siloxane and side type that mean molecule quantity is 3000~10000 One kind in amino polydimethyl siloxane.
5. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described multi-hydroxy carboxy acid is one kind in dihydromethyl propionic acid, dimethylolpropionic acid and tartaric acid.
6. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described organo-metallic catalyst is stannous octoate, dibutyl tin dilaurate, lead octoate and two acetic acid di-n-butyl tins In one kind.
7. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described crosslinking agent is trimethylolpropane；
Described nertralizer is triethylamine, trimethylamine, N, one kind in N- dimethylethanolamines, diethanol amine and triethanolamine.
8. organosilicon according to claim 1 and the dual modified polyester-type aqueous polyurethane of four-needle-like zinc oxide disperse Body, it is characterised in that：
Described chain extender is 1,4- butanediols, ethylene glycol, propane diols, hexylene glycol, cyclohexanediol, the hydroxyl ethyl ester of terephthalic acid (TPA) two At least one of with trimethyolol propane monoallyl ether；
Described defoamer is one in organic silicon defoamer, mineral oil defoaming agent and polar organic compounds class defoamer Kind.
9. the dual modified polyester-type aqueous polyurethane of organosilicon and four-needle-like zinc oxide described in any one of claim 1~8 The preparation method of dispersion, it is characterised in that comprise the following steps：
Take 1~8 mass parts gamma-aminopropyl-triethoxy-silane be modified four-needle-like zinc oxide, 13~91 mass parts diisocyanate, 100 mass parts PEPAs, 10~25 mass parts amido silicon oils, under nitrogen protection, -10~0 DEG C of stirring reaction 0.5~ 1 hour, 0~0.5 mass parts organo-metallic catalyst is then added, is warming up to 50~90 DEG C of stirring reactions 1~2 hour, then is added Enter 8~16 mass parts multi-hydroxy carboxy acids and 0.3~10 mass parts crosslinking agent, continue reaction 2~4 hours, with acetone viscosity reduction, obtain Prepolymer；Room temperature is then cooled to, 6.2~18 mass parts nertralizers is added and neutralizes into salt, add water to be stirred vigorously emulsification；After emulsification 1~8 mass parts chain extender, 0.2~2.0 mass parts defoamer are added, stirs 20~60 minutes at 20~60 DEG C, finally depressurizes The acetone in removing system is evaporated, polyester-type aqueous polyurethane dispersion is made.
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