CN104844778A - Organic silicon and four-needle zinc oxide double modified polyester-type aqueous polyurethane dispersion, preparation and application - Google Patents

Organic silicon and four-needle zinc oxide double modified polyester-type aqueous polyurethane dispersion, preparation and application Download PDF

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CN104844778A
CN104844778A CN201510223444.6A CN201510223444A CN104844778A CN 104844778 A CN104844778 A CN 104844778A CN 201510223444 A CN201510223444 A CN 201510223444A CN 104844778 A CN104844778 A CN 104844778A
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zinc oxide
needle
aqueous polyurethane
polyurethane dispersion
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CN104844778B (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 invention discloses an organic silicon and four-needle zinc oxide double modified polyester-type aqueous polyurethane dispersion, preparation and application. The dispersion comprises, by weight, 1-8 parts of gamma-aminopropyltriethoxysilane modified four-needle zinc oxide, 100 parts of polyester polyol, 13-91 parts of diisocyanate, 10-25 parts of amino silicone oil, 0-0.5 part of organo-metallic catalyst, 8-16 parts of polyhydroxy carboxylic acid, 0.3-10 parts of cross-linking agents, 6.2-18 parts of neutralizing agents, 1-8 parts of chain extenders and 0.2-2.0 parts of defoaming agents. Amino on the surface of the gamma-aminopropyltriethoxysilane modified four-needle zinc oxide can be connected onto a polyurethane molecule chain through chemical reaction, compatibility is improved, and uniform dispersion of four-needle zinc oxide is facilitated. The prepared dispersion has fine thermal property, mechanical property, water resistance, antistatic property and ultraviolet ageing resistance.

Description

A kind of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide and Synthesis and applications
Technical field
The invention belongs to chemical field, relate to a kind of synthesis of polyester type aqueous polyurethane dispersion, be specifically related to a kind of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide and preparation method and application.
Background technology
Aqueous polyurethane (WPU) is the polyurethane system using water to replace organic solvent as dispersion medium, because it is nontoxic, do not fire and free of contamination characteristic just progressively replaces conventional solvent type polyurethane, becomes the important directions of polyurethane industrial development.Aqueous polyurethane can be widely used in coating, tackiness agent, fabric coating and finishing composition, paper and Fiber strength agent, hide finishes.But often there is the shortcomings such as resistance to acids and bases, thermostability, ultraviolet-resistant aging and bad mechanical property in single aqueous polyurethane.Aqueous polyurethane is divided into polyester type and polyester type two class, and wherein the water tolerance of polyester type aqueous polyurethane is badly in need of improving.
Organosilicon material, owing to itself having heatproof, weather-proof, the special performance such as electrical insulation capability, low surface tension, low surface energy and physiological inertia, is often used to modified polyurethane, to improve its thermotolerance, water tolerance, weathering resistance etc.But because the consistency of organosilicon and urethane is bad, therefore usually can reduce the mechanical property of material.
Four acicular type zinc oxide crystal whisker (T-ZnOw) was found the forties in 20th century, was the whisker uniquely in current whisker family with regular three-D space structure.Four acicular type zinc oxide crystal whisker is the toughener that a class is fabulous, can give matrix material good mechanical property; And, because of its semiconductive, inhale imparted and highly dense property, prepared matrix material can be made to have good static resistance, resistance to deterioration and damping property.Though four-needle-like zinc oxide can improve the multiple performance of urethane, but the consistency of inorganic particulate and urethane is bad, be difficult to realize good dispersion, therefore its modified effect to urethane can be reduced.
Adopt organosilicon and the common modified aqueous polyurethane of four-needle-like zinc oxide, the better thermotolerance of urethane, surface property, mechanical property and weathering resistance can be given, thus expand its range of application.
Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, primary and foremost purpose of the present invention is to provide a kind of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide.
Another object of the present invention is to provide the preparation method of above-mentioned organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide.
Another object of the present invention is to provide the application of above-mentioned organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide.
Object of the present invention is achieved through the following technical solutions:
Organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, comprise following component: 1 ~ 8 mass parts γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 100 mass parts polyester polyols, 13 ~ 91 mass parts vulcabond, 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 linking agent, 6.2 ~ 18 mass parts neutralizing agents, 1 ~ 8 mass parts chainextender, 0.2 ~ 2.0 mass parts defoamer.
Described vulcabond is selected from tolylene diisocyanate (TDI), ditan-4,4'-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), xylylene diisocyanate (XDI), 1, one in 4-cyclohexyl diisocyanate (CHDI) and naphthalene-1,5-vulcabond (NDI).Wherein, preferred vulcabond is tolylene diisocyanate (TDI) or ditan-4,4'-vulcabond (MDI).
Described polyester polyol be selected from average functionality be greater than 2 and molecular-weight average be 400 ~ 6000 hexanodioic acid system polyester polyol, pimelic acid system polyester polyol, suberic acid system polyester polyol, pentanedioic acid system polyester polyol, polyester polyol of sebacic acid series, oxalic acid series polyester polyol, Succinic Acid Polyester Polyols polyester polyol, polycaprolactone polyol, polycarbonate polyol, cis-butenedioic anhydride polyester polyol, benzoic anhydride polyester polyol, to the one in benzene polyester polyol and random copolymerization ester polyol.Wherein, polyester polyol is preferably hexanodioic acid system polyester polyol or polycaprolactone polyol.
Described amido silicon oil be selected from molecular-weight average be 3000 ~ 10000 double ended type amino polydimethyl siloxane and side type amino polydimethyl siloxane in one.
Described organo-metallic catalyst is selected from the one in stannous octoate, dibutyl tin dilaurate, lead octoate 36 and two acetic acid di-n-butyl tins; Wherein, organo-metallic catalyst is preferably dibutyl tin dilaurate.
Described multi-hydroxy carboxy acid is selected from the one in dimethylol propionic acid, dimethylolpropionic acid and tartrate.
Described linking agent is selected from TriMethylolPropane(TMP).
Described neutralizing agent is selected from the one in triethylamine, Trimethylamine 99, N, N-dimethylethanolamine, diethanolamine and trolamine.
Described chainextender is selected from least one in BDO, ethylene glycol, propylene glycol, hexylene glycol, cyclohexanediol, terephthalic acid dihydroxy ethyl ester and TriMethylolPropane(TMP) mono allyl ether; Be more preferably BDO.
Described defoamer is selected from the one in silicone based defoamer, mineral oil defoaming agent and polar organic compounds defoamer.Be more preferably silicone based defoamer.
The preparation method of described γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, comprises following steps:
(1) 12 ~ 14 mass parts dehydrated alcohols, 2 ~ 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 ~ 1 hour, obtain γ-aminopropyl triethoxysilane mixed solution;
(2) mixed with 150 ~ 300 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 ~ 1 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide;
(3) the γ-aminopropyl triethoxysilane mixed solution that 5 ~ 20 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 175 ~ 350 mass parts steps (2), return stirring 1.5 ~ 3 hours in 60 ~ 80 DEG C of oil baths; Reaction terminates rear suction filtration, and with absolute ethanol washing 3 ~ 5 times, vacuum-drying 24 ~ 48 hours at 60 ~ 70 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
The preparation method of described organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, comprises the steps:
Get 1 ~ 8 mass parts γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 13 ~ 91 mass parts vulcabond, 100 mass parts polyester polyols, 10 ~ 25 mass parts amido silicon oils; under nitrogen protection;-10 ~ 0 DEG C of stirring reaction 0.5 ~ 1 hour; then 0 ~ 0.5 mass parts organo-metallic catalyst is added; be warming up to 50 ~ 90 DEG C of stirring reactions 2 ~ 3 hours; add 8 ~ 16 mass parts multi-hydroxy carboxy acids and 0.3 ~ 10 mass parts linking agent again; continue reaction 2 ~ 4 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 6.2 ~ 18 mass parts neutralizing agents and salify, the vigorous stirring that adds water emulsification.Add 1 ~ 8 mass parts chainextender, 0.2 ~ 2.0 mass parts defoamer after emulsification, stir 20 ~ 60 minutes at 20 ~ 60 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Described vulcabond is selected from tolylene diisocyanate (TDI), ditan-4,4'-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), xylylene diisocyanate (XDI), 1, one in 4-cyclohexyl diisocyanate (CHDI) and naphthalene-1,5-vulcabond (NDI).Wherein, preferred vulcabond is tolylene diisocyanate (TDI) or ditan-4,4'-vulcabond (MDI).
Described polyester polyol be selected from average functionality be greater than 2 and molecular-weight average be 400 ~ 6000 hexanodioic acid system polyester polyol, pimelic acid system polyester polyol, suberic acid system polyester polyol, pentanedioic acid system polyester polyol, polyester polyol of sebacic acid series, oxalic acid series polyester polyol, Succinic Acid Polyester Polyols polyester polyol, polycaprolactone polyol, polycarbonate polyol, cis-butenedioic anhydride polyester polyol, benzoic anhydride polyester polyol, to at least one in benzene polyester polyol and random copolymerization ester polyol.Wherein, polyester polyol is preferably hexanodioic acid system polyester polyol or polycaprolactone polyol.
Described amido silicon oil be selected from molecular-weight average be 3000 ~ 10000 double ended type amino polydimethyl siloxane and side type amino polydimethyl siloxane in one.
Described organo-metallic catalyst is selected from the one in stannous octoate, dibutyl tin dilaurate, lead octoate 36 and two acetic acid di-n-butyl tins; Wherein, organo-metallic catalyst is preferably dibutyl tin dilaurate.
Described multi-hydroxy carboxy acid is selected from the one in dimethylol propionic acid, dimethylolpropionic acid and tartrate.
Described linking agent is selected from TriMethylolPropane(TMP).
Described neutralizing agent is selected from the one in triethylamine, Trimethylamine 99, N, N-dimethylethanolamine, diethanolamine and trolamine.
Described chainextender is selected from least one in BDO, ethylene glycol, propylene glycol, hexylene glycol, cyclohexanediol, terephthalic acid dihydroxy ethyl ester and TriMethylolPropane(TMP) mono allyl ether; Be more preferably BDO.
Described defoamer is selected from the one in silicone based defoamer, mineral oil defoaming agent and polar organic compounds defoamer.Be more preferably silicone based defoamer.
The preparation method of described γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, comprises following steps:
(1) 12 ~ 14 mass parts dehydrated alcohols, 2 ~ 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 ~ 1 hour, obtain γ-aminopropyl triethoxysilane mixed solution;
(2) mixed with 150 ~ 300 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 ~ 1 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide;
(3) the γ-aminopropyl triethoxysilane mixed solution that 5 ~ 20 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 175 ~ 350 mass parts steps (2), return stirring 1.5 ~ 3 hours in 60 ~ 80 DEG C of oil baths; Reaction terminates rear suction filtration, and with absolute ethanol washing 3 ~ 5 times, vacuum-drying 24 ~ 48 hours at 60 ~ 70 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Described organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide can be applicable to woodwork coating, electrocoating paint, building coating, paper process coating, glass fiber coating, electrocoating paint etc.
The present invention, relative to prior art, has following advantage and effect:
(1) the polyester type aqueous polyurethane dispersion of the organosilicon prepared in the present invention and the common modification of four-needle-like zinc oxide, makes not only have good thermal property, mechanical property, water tolerance but also have static resistance, anti-ultraviolet ageing ability.
(2) the present invention adopts γ-aminopropyl triethoxysilane to carry out modification to four-needle-like zinc oxide, makes four-needle-like zinc oxide surface be connected to a large amount of silane coupling agent, increases the consistency of four-needle-like zinc oxide and urethane.In addition, γ-aminopropyl triethoxysilane coupling agent is in modification four-needle-like zinc oxide process, and its amino has neither part nor lot in reaction.The amino remained is connected on polyurethane molecular chain by chemical reaction, which further improves the consistency of four-needle-like zinc oxide and polyurethane matrix.
(3) the present invention adds four-needle-like zinc oxide than common organic silicon modified polyurethane system, the pin of four-needle-like zinc oxide can stop organosilyl gathering to a certain extent, thus the degree that is separated reduced between organosilicon and urethane, and then improve the overall performance of material.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In following examples, each performance test methods is as follows:
TG adopts the resistance to TG209F3-Brooker TENSOR 27 ftir Analysis combination analysis instrument test of speeding of Germany, N 2atmosphere, temperature rise rate 10 DEG C/min.
The mensuration of water tolerance adopts infusion method, namely takes a certain amount of glued membrane (W 1), be immersed in about 25 DEG C distilled water, take out, wipe surface-moisture fast with filter paper after 24h, weigh (W immediately 2), water-intake rate (P) is calculated by following formula: P=[(W 2-W 1)/W 1] × 100%.
Elongation at break and tensile strength adopt Shenzhen newly to think carefully material tests company limited CMT4503 electronic tensile machine, according to GB/T 13022-1991 standard testing.
Ultraviolet ageing adopts Shanghai one permanent company BHO-401A climatic chamber, and digestion time is 168 hours.
Embodiment 1
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 12 mass parts dehydrated alcohols, 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 150 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 5 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 175 mass parts steps (2), return stirring 1.5 hours in 70 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 3 times, vacuum-drying 48 hours at 60 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
Be 2000 by 1g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide and 18g tolylene diisocyanate, 100g molecular-weight average; hydroxyl value is the polycaprolactone diols of 55-58,10g molecular weight is the α of 5000; the polydimethylsiloxane of ω-two aminopropyl end-blocking; under nitrogen protection;-10 DEG C of stirring reactions 1 hour; then 0.5g stannous octoate is added; be warming up to 70 DEG C of stirring reactions 2 hours; add 8g dimethylol propionic acid and 1g TriMethylolPropane(TMP) again; continue reaction 4 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 6.2g triethylamine and salify, the vigorous stirring that adds water emulsification.Add 3g BDO and the silicone based defoamer of 0.2g after emulsification, stir 40 minutes at 50 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 368.5 DEG C, and water-intake rate is 6.5%, and elongation at break is 380%, and tensile strength is 16MPa.After ultraviolet ageing, its elongation at break is 361%, and tensile strength is 13.8MPa.
Embodiment 2
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 14 mass parts dehydrated alcohols, 2 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 1 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 300 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 1 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 20 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 325 mass parts steps (2), return stirring 3 hours in 60 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 5 times, vacuum-drying 24 hours at 70 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
By 2.5g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 29g ditan-4, 4 '-vulcabond, 100g molecular-weight average is 3000, hydroxyl value is the poly-adipate glycol trihydroxymethylpropanyl ester polyvalent alcohol of 50-55, 25g molecular weight is the aminoethylaminopropyl polydimethylsiloxane of 6000, under nitrogen protection, 0 DEG C of stirring reaction 0.5 hour, then 0.05g dibutyl tin dilaurate is added, be warming up to 80 DEG C of stirring reactions 1 hour, add 16g dimethylolpropionic acid and 10g TriMethylolPropane(TMP) again, continue reaction 3 hours, use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 6.4g Trimethylamine 99 and salify, the vigorous stirring that adds water emulsification.Add 2g ethylene glycol and the silicone based defoamer of 0.8g after emulsification, stir 60 minutes at 20 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 385.2 DEG C, and water-intake rate is 7.3%, and elongation at break is 295%, and tensile strength is 23.4MPa.After ultraviolet ageing, its elongation at break is 278%, and tensile strength is 19.6MPa.
Embodiment 3
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 13 mass parts dehydrated alcohols, 3 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.8 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 220 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.7 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 18 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 245 mass parts steps (2), return stirring 2 hours in 80 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 4 times, vacuum-drying 36 hours at 65 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
Be 500 by 4g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 91g isophorone diisocyanate, 100g molecular-weight average; hydroxyl value is the PCDL of 220-230,20g molecular weight is the α of 10000; the polydimethylsiloxane of ω-two aminopropyl end-blocking; under nitrogen protection;-10 DEG C of stirring reactions 0.5 hour; then 0.3g lead octoate 36 is added; be warmed up to 50 DEG C of stirring reactions 1 hour; add 16g tartrate and 0.5g TriMethylolPropane(TMP) again; continue reaction 2 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add 18g N, in N-dimethylethanolamine and salify, the vigorous stirring that adds water emulsification.Add 2g propylene glycol and 1.0g mineral oil defoaming agent after emulsification, stir 30 minutes at 30 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 392.1 DEG C, and water-intake rate is 5.8%, and elongation at break is 201%, and tensile strength is 28.4MPa.After ultraviolet ageing, its elongation at break is 164%, and tensile strength is 25.6MPa.
Embodiment 4
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 12 mass parts dehydrated alcohols, 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 200 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 15 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 225 mass parts steps (2), return stirring 2.5 hours in 80 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 4 times, vacuum-drying 40 hours at 65 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
Be 6000 by 8g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 13g isophorone diisocyanate, 100g molecular-weight average; the aminoethylaminopropyl polydimethylsiloxane that the poly-suberic acid glycol ether esterdiol that hydroxyl value is 16-20,18g molecular weight are 3000; under nitrogen protection;-5 DEG C of stirring reactions 0.7 hour; then 0.4g bis-acetic acid di-n-butyl tin is added; be warming up to 80 DEG C of stirring reactions 1 hour; add 12g dimethylol propionic acid and 0.3g TriMethylolPropane(TMP); continue reaction 3 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 9.5g diethanolamine and salify, the vigorous stirring that adds water emulsification.Add 1g hexylene glycol and 1.4g mineral oil defoaming agent after emulsification, stir 50 minutes at 60 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 372.8 DEG C, and water-intake rate is 7.1%, and elongation at break is 352%, and tensile strength is 17.9MPa, and after ultraviolet ageing, its elongation at break is 248%, and tensile strength is 15.4MPa.
Embodiment 5
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 12 mass parts dehydrated alcohols, 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 200 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 8 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 225 mass parts steps (2), return stirring 2 hours in 80 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 3 times, vacuum-drying 30 hours at 65 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
Be 400 by 3g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide and 83g PPDI and 100g molecular-weight average; hydroxyl value is the polydiethylene glycol sebacate glycol of 275-285,12g molecular weight is the α of 4000; the polydimethylsiloxane of ω-two aminopropyl end-blocking; under nitrogen protection;-10 DEG C of stirring reactions 0.5 hour; then 50 DEG C of stirring reactions 1 hour is warming up to; add 12g dimethylol propionic acid and 1.5g TriMethylolPropane(TMP); continue reaction 3 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 13.3g trolamine and salify, the vigorous stirring that adds water emulsification.Add 2g cyclohexanediol after emulsification, 2g terephthalic acid dihydroxy ethyl ester and 1.7g polar organic compounds defoamer, stir 50 minutes at 60 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 393.8 DEG C, and water-intake rate is 8.6%, and elongation at break is 240%, and tensile strength is 25.7MPa.After ultraviolet ageing, its elongation at break is 185%, and tensile strength is 23.3MPa.
Embodiment 6
One, the preparation of γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide
(1) 12 mass parts dehydrated alcohols, 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 hour, obtain γ-aminopropyl triethoxysilane mixed solution.
(2) mixed with 200 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide.
(3) the γ-aminopropyl triethoxysilane mixed solution that 10 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 225 mass parts steps (2), return stirring 2 hours in 80 DEG C of oil baths.Reaction terminates rear suction filtration, and with absolute ethanol washing 3 times, vacuum-drying 24 hours at 65 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
Two, the preparation of organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide
Be 1000 by 1.5g γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 36g tolylene diisocyanate, 100g molecular-weight average, hydroxyl value be 110-115 to benzene polyester diol; 10g molecular weight is the α of 8000; the polydimethylsiloxane of ω-two aminopropyl end-blocking; under nitrogen protection;-5 DEG C of stirring reactions 1 hour; then 0.4g dibutyl tin dilaurate is added; be warming up to 70 DEG C of stirring reactions 1 hour; add 13g dimethylol propionic acid and 2.5g TriMethylolPropane(TMP); continue reaction 2 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 9.8g triethylamine and salify, the vigorous stirring that adds water emulsification.Add 8g TriMethylolPropane(TMP) mono allyl ether and 2.0g polar organic compounds defoamer after emulsification, stir 25 minutes at 30 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Recording its maximum heat weightless temperature is 385.4 DEG C, and water-intake rate is 7.1%, and elongation at break is 366%, and tensile strength is 24.1MPa, and after ultraviolet ageing, its elongation at break is 354%, and tensile strength is 21.3MPa.
Comparative example 1
Table 1
Wherein, in table 1, sample A is pure polyester type aqueous polyurethane; its preparation method is: be 2000 by 18g tolylene diisocyanate, 100g molecular-weight average, and hydroxyl value is the polycaprolactone diols of 55-58,0.5g stannous octoate; under nitrogen protection; 70 DEG C of stirring reactions 2 hours, then add 8g dimethylol propionic acid and 1g TriMethylolPropane(TMP), continue reaction 4 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 6.2g triethylamine and salify, the vigorous stirring that adds water emulsification.Add 3g BDO and the silicone based defoamer of 0.2g after emulsification, stir 40 minutes at 50 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Can be found out by table 1, compared with unmodified pure urethane (sample A), the maximum heat weightless temperature of the organosilicon that embodiment 1 is obtained and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide enlarges markedly, water-intake rate significantly reduces, and tensile strength improves.After ultraviolet ageing, reducing all appears in the tensile strength of two kinds of samples and elongation at break, but the reduction degree of embodiment 1 is less than sample A.This comparative example illustrates that organosilicon prepared by the present invention and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide have good thermal property, water tolerance, mechanical property and anti-uv-ray.
Comparative example 2
Table 2
Wherein, in table 2, sample B is pure polyester type aqueous polyurethane; its preparation method is: be 3000 by 29g ditan-4,4 '-vulcabond, 100g molecular-weight average, and hydroxyl value is poly-adipate glycol trihydroxymethylpropanyl ester polyvalent alcohol, the 0.05g dibutyl tin dilaurate of 50-55; under nitrogen protection; 80 DEG C of stirring reactions 1 hour, then add 16g dimethylolpropionic acid and 10g TriMethylolPropane(TMP), continue reaction 3 hours; use acetone viscosity reduction, obtain prepolymer.Be cooled to room temperature subsequently, add in 6.4g Trimethylamine 99 and salify, the vigorous stirring that adds water emulsification.Add 2g ethylene glycol and the silicone based defoamer of 0.8g after emulsification, stir 60 minutes at 20 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.Then by its curtain coating in the template of horizontal, seasoning film forming under room temperature, then vacuum-drying is to after permanent quality, carries out performance test.
Can be found out by table 2, compared with unmodified pure urethane (sample B), the maximum heat weightless temperature of the organosilicon that embodiment 2 is obtained and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide enlarges markedly, water-intake rate significantly reduces, and tensile strength improves.After ultraviolet ageing, reducing all appears in the tensile strength of two kinds of samples and elongation at break, but the reduction degree of embodiment 2 is less than sample B.This comparative example illustrates that organosilicon prepared by the present invention and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide have good thermal property, water tolerance, mechanical property and anti-uv-ray.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. organosilicon and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that comprising following component: 1 ~ 8 mass parts γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 100 mass parts polyester polyols, 13 ~ 91 mass parts vulcabond, 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 linking agent, 6.2 ~ 18 mass parts neutralizing agents, 1 ~ 8 mass parts chainextender, 0.2 ~ 2.0 mass parts defoamer.
2. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
The preparation method of described γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, comprises following steps:
(1) 12 ~ 14 mass parts dehydrated alcohols, 2 ~ 4 mass parts deionized waters and 4 mass parts γ-aminopropyl triethoxysilanes are mixed, be at room temperature hydrolyzed 0.5 ~ 1 hour, obtain γ-aminopropyl triethoxysilane mixed solution;
(2) mixed with 150 ~ 300 mass parts dehydrated alcohols by 25 mass parts four-needle-like zinc oxides, ultrasonic disperse 0.5 ~ 1 hour, obtains the alcohol dispersion liquid of four-needle-like zinc oxide;
(3) the γ-aminopropyl triethoxysilane mixed solution that 5 ~ 20 mass parts steps (1) are obtained is added in the alcohol dispersion liquid of the obtained four-needle-like zinc oxide of 175 ~ 350 mass parts steps (2), return stirring 1.5 ~ 3 hours in 60 ~ 80 DEG C of oil baths; Reaction terminates rear suction filtration, and with absolute ethanol washing 3 ~ 5 times, vacuum-drying 24 ~ 48 hours at 60 ~ 70 DEG C, obtains γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide.
3. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described vulcabond is tolylene diisocyanate, ditan-4,4'-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, PPDI, xylylene diisocyanate, 1, one in 4-cyclohexyl diisocyanate and naphthalene-1,5-vulcabond.
4. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described polyester polyol be average functionality be greater than 2 and molecular-weight average be 400 ~ 6000 hexanodioic acid system polyester polyol, pimelic acid system polyester polyol, suberic acid system polyester polyol, pentanedioic acid system polyester polyol, polyester polyol of sebacic acid series, oxalic acid series polyester polyol, Succinic Acid Polyester Polyols polyester polyol, polycaprolactone polyol, polycarbonate polyol, cis-butenedioic anhydride polyester polyol, benzoic anhydride polyester polyol, to at least one in benzene polyester polyol and random copolymerization ester polyol.
5. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described amido silicon oil to be molecular-weight average be 3000 ~ 10000 double ended type amino polydimethyl siloxane and side type amino polydimethyl siloxane in one.
6. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described multi-hydroxy carboxy acid is the one in dimethylol propionic acid, dimethylolpropionic acid and tartrate.
7. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described organo-metallic catalyst is the one in stannous octoate, dibutyl tin dilaurate, lead octoate 36 and two acetic acid di-n-butyl tins.
8. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described linking agent is TriMethylolPropane(TMP);
Described neutralizing agent is the one in triethylamine, Trimethylamine 99, N, N-dimethylethanolamine, diethanolamine and trolamine.
9. organosilicon according to claim 1 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that:
Described chainextender is at least one in BDO, ethylene glycol, propylene glycol, hexylene glycol, cyclohexanediol, terephthalic acid dihydroxy ethyl ester and TriMethylolPropane(TMP) mono allyl ether;
Described defoamer is the one in silicone based defoamer, mineral oil defoaming agent and polar organic compounds defoamer.
10. the preparation method of the organosilicon described in any one of claim 1 ~ 9 and the dual modified polyester type aqueous polyurethane dispersion of four-needle-like zinc oxide, is characterized in that comprising the steps:
Get 1 ~ 8 mass parts γ-aminopropyl triethoxysilane modification four-needle-like zinc oxide, 13 ~ 91 mass parts vulcabond, 100 mass parts polyester polyols, 10 ~ 25 mass parts amido silicon oils, under nitrogen protection,-10 ~ 0 DEG C of stirring reaction 0.5 ~ 1 hour, then 0 ~ 0.5 mass parts organo-metallic catalyst is added, be warming up to 50 ~ 90 DEG C of stirring reactions 1 ~ 2 hour, add 8 ~ 16 mass parts multi-hydroxy carboxy acids and 0.3 ~ 10 mass parts linking agent again, continue reaction 2 ~ 4 hours, use acetone viscosity reduction, obtain prepolymer; Be cooled to room temperature subsequently, add in 6.2 ~ 18 mass parts neutralizing agents and salify, the vigorous stirring that adds water emulsification; Add 1 ~ 8 mass parts chainextender, 0.2 ~ 2.0 mass parts defoamer after emulsification, stir 20 ~ 60 minutes at 20 ~ 60 DEG C, the acetone in last reduction vaporization removing system, obtained polyester type aqueous polyurethane dispersion.
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张力元等: ""四针状氧化锌晶须对形状记忆聚氨酯的力学影响"", 《浙江理工大学学报》 *
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EP3444286A4 (en) * 2016-04-14 2019-12-25 DIC Corporation Water-based urethane resin composition and synthetic leather
TWI719185B (en) * 2016-04-14 2021-02-21 日商迪愛生股份有限公司 Water-based urethane resin composition and synthetic leather
CN112143470A (en) * 2019-06-28 2020-12-29 中国石油化工股份有限公司 Plugging material, preparation method thereof and plugging agent
CN110628316A (en) * 2019-10-14 2019-12-31 无锡新而奇化工科技有限公司 Tetrapod-like zinc oxide whisker modified polyurethane resin coating and preparation method thereof
CN110628316B (en) * 2019-10-14 2021-04-02 无锡新而奇化工科技有限公司 Tetrapod-like zinc oxide whisker modified polyurethane resin coating and preparation method thereof

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