CN106947036A - A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion and preparation method thereof - Google Patents
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, including following raw material components：Modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water, modified Nano particle is reacted by inorganic nano-particle and unsaturated acids to be made, and inorganic nano-particle is made by metal salt and ester reaction.The invention also discloses the preparation method of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, including：Metal salt and esters form inorganic nano-particle in aqueous phase, inorganic nano-particle reacts to form modified Nano particle with unsaturated acids, and Raolical polymerizable occurs in aqueous phase and forms inorganic nanometer modified vinyl chloride-propylene analog derivative copolymer emulsion for modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated polyether class and auxiliary agent.Reaction temperature is low in present copolymer emulsion preparation process, with excellent film forming and surface and interface performance.
Description
Technical field
The present invention relates to a kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion and preparation method thereof.
Background technology
Polyvinylidene chloride and its copolymer have the excellent physico-chemical property such as excellent chemical stability, solvent resistance, fire-retardant
Meanwhile, also there is high barrier to gas or steam.It is widely used in chemical industry, light industry, packaging for foodstuff, medical packaging, puts
Put, the gas high barrier field such as automobile.
At present, the preparation method of polyvinylidene chloride mainly has solution copolymerization, aqueous phase copolymerization and newborn phase copolymerization.Solution copolymerization is present
Reaction time is long, and conversion ratio is low, the defect such as solvent internal circulating load is big；Aqueous phase copolymerization has different dissolvings due to comonomer in water
The difference of degree and proportion, obtained copolymer composition homogeneity is poor；Emulsion polymerization has product form uniform, copolymer quality
Good, the advantage such as conversion ratio height, therefore, newborn phase-polymerization can design spaces with bigger.
The content of the invention
The invention aims to overcome the problem of prior art is present, there is provided a kind of inorganic nanometer modified vinyl chloride-propylene class
The preparation method of derivative-copolyether emulsion, this method is by changing reactant feed and solvent species, and preparing has valency
Lattice are low, reaction temperature is low, good film-forming property, the emulsion of surface and interface excellent performance.
The purpose of the present invention is achieved through the following technical solutions：
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, including following raw material components：Modification is received
Rice corpuscles, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water, described modified Nano particle,
Initiator, vinyl chloride, propylene analog derivative, unsaturated ether, the mass ratio of auxiliary agent and water are 0.001~30：0.001~
5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~99.99；Wherein, described modification is received
Rice corpuscles is reacted by inorganic nano-particle and unsaturated acids to be made, and described inorganic nano-particle and the mass ratio of unsaturated acids are
0.001~30：0.001~99.99；Described inorganic nano-particle is made by metal salt and ester reaction, described metal salt and
The mass ratio of esters is 0.001~50：0.001~99.99.
Described coating is by following preparation method system with inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion
：(1) it is, 0.001~50 according to mass ratio by metal salt, esters and water：0.001~99.99：0.001~99.99 adds
Into reactor, stirring, 50~160 DEG C of maintenance system temperature, vacuum -0.01~-0.1MPa, in heating reduced-pressure backflow bar
2~30h is reacted under part, product obtains inorganic nano-particle through filtering, washing, dry；(2), inorganic nano-particle and not
Saturated acid is according to mass ratio 0.001~30：0.001~99.99 in 80~180 DEG C of temperature, vacuum -0.01~-0.1MPa, plus
2~30h is reacted under the conditions of hot reduced-pressure backflow, product washs, dried, that is, obtain modified Nano particle through filtering；(3), change
Property nano-particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water according to mass ratio 0.001~
30：0.001~5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~99.99, in temperature
20~100 DEG C, nitrogen protection 0.1~20h of lower reaction obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-polyethers common
Copolymer emulsion.
The preparation method of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion of the present invention, including under
Row step：
(1) it is, 0.001~50 according to mass ratio by metal salt, esters and water：0.001~99.99：0.001~99.99 is added to
In reactor, stirring, 50~160 DEG C of maintenance system temperature, vacuum -0.01~-0.1MPa, in heating reduced-pressure backflow condition
2~30h of lower reaction, product obtains inorganic nano-particle through filtering, washing, dry；Described washing methods be ethanol and
Water is alternately washed, and the purpose of washing is in order to remove in reaction system impurity such as, esters, metal salt, alcohol etc.；To adding water (or second
Alcohol) measure without particular/special requirement.
(2), inorganic nano-particle and unsaturated acids are according to mass ratio 0.001~30：0.001~99.99 temperature 80~
180 DEG C, heating reduced-pressure backflow reacts 2~30h under the conditions of vacuum -0.01~-0.1MPa, product is washing, dry through filtering
It is dry, that is, obtain modified Nano particle；The purpose of washing is in order to remove unreacted acid.
(3), modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water are according to matter
Measure ratio 0.001~30：0.001~5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~
99.99, in 20~100 DEG C of temperature, nitrogen protection 0.1~20h of lower reaction obtains inorganic nano by Raolical polymerizable
Modified vinyl chloride -- propylene analog derivative-copolyether emulsion.
In step (1), the mass ratio of described metal salt, esters and water is preferably 1~2：1~10：1~5, further preferably
For 1：2~2.5：1~2；The described temperature for preparing inorganic nano-particle is preferably 60~90 DEG C, and vacuum is preferably-
0.06~-0.09MPa, the reaction time is preferably 2~8h.
In step (2), described inorganic nano-particle and the mass ratio of unsaturated acids are preferably 1~30：1~75, it is further excellent
Elect 1 as：2~5；The described temperature for preparing modified Nano particle is preferably 120~175 DEG C, and vacuum is preferably -0.04~-
0.09MPa, the reaction time is preferably 5~10h.
In step (3), described modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, help
The mass ratio of agent and water is preferably 1~30：1~5：1~90：1~30：1~15：1~15：1~90, further preferably
For 1：0.2~0.35：7~9：1.5~2：0.6~0.8：1~3：6~12；It is described prepare inorganic nanometer modified vinyl chloride-
The temperature of-propylene analog derivative-copolyether emulsion is preferably 50~75 DEG C, and the reaction time is preferably 4.5~7.5h.
Described metal salt be silicon salt, titanium salt, calcium salt, magnesium salts, aluminium salt, boron salt, pink salt, zinc salt, barium salt in one kind or
Several mixtures, preferably sodium metasilicate.
Described esters are methyl formate, Ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, acetic acid
Propyl ester, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyric acid
One or more of mixtures of propyl ester, butyl butyrate, preferably ethyl acetate.
Described unsaturated acids is acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylate, butenoic acid, methyl butene
Acid, preferably one or more of mixtures of ethyl butenoic acid, propyl group butenoic acid, acrylic acid.
Described initiator is azo-initiator, peroxide initiator, redox initiator, the preferably isobutyl of azo two
Nitrile, peroxidating two acyl, persulfate, dibenzoyl peroxide, persulfate-acid sulfite or DMA
One or more of mixtures, preferably nitrogen bis-isobutyronitrile.
Described vinyl chloride is one or more of mixing of vinyl chloride, 1,1- dichloroethylene, 1,2- dichloroethylene, trichloro ethylene
The mixture of thing, preferably vinylidene chloride or 1,2-dichloroethene and trichloro ethylene.
The propylene analog derivative is acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylate, methyl acrylate, first
Base methyl acrylate, ethyl methyl acrylate, propylacrylate methyl esters, ethyl acrylate, EMA, ethyl third
Olefin(e) acid ethyl ester, propylacrylate ethyl ester, propyl acrylate, propyl methacrylate, ethyl propylene propyl propionate, propylacrylate
Propyl ester, acrylamide, Methacrylamide, ethyl acrylamide, propylacrylamide, acrylonitrile, methacrylonitrile, second
One or more of mixtures of base acrylonitrile, propyl group acrylonitrile, preferably methyl methacrylate.
The unsaturated polyether class is polyethylene glycol, one or more of mixtures of PolyTHF.
Described auxiliary agent is surfactant (dodecyl sodium sulfate, neopelex, stearic acid), antioxidant
(monooctyl ester of phosphorous acid three, triphenyl phosphite, phosphorous acid, 2,6 di tert butyl 4 methyl phenol, tert-butylhydroquinone),
Ultra-violet absorber (2- (2- hydroxy-5-methyl bases phenyl) BTA, 2,4 dihydroxyl benzophenone, 2- hydroxyl -4- methoxyl groups two
Benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2'- hydroxyls -3', 5'- di-tert-butyl-phenyl) -5- chlorinations BTA, single benzene
Formic acid resorcinol, 2,2- thiobis (4- t-octyl phenol epoxide) nickel, three (1,2,2,6,6- pempidine base) phosphite esters), it is anti-
Heavy agent is (organobentonite, castor oil or derivatives thereof, polyolefin-wax, the 1-METHYLPYRROLIDONE solution of modified polyurea, poly-
Amide waxe), dispersant (OP-10, paraffin class dispersant, metal soap pigment dispersing agent, polyvinyl alcohol 217), coupling
Two or more mixture of agent (organochromium complexes, silanes, titanate ester, aluminic acid compound).
Inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion viscosity average molecular weigh of the present invention is 10,000-100
Ten thousand.
Inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion coating of the present invention is prepared in substrate surface
The application of hydrophobic membrane or automatically cleaning film.The present invention is coated on the inorganic nanometer modified chlorine that substrate surface prepares hydrophobic membrane or automatically cleaning film
Ethylene-propylene analog derivative-copolyether emulsion viscosity average molecular weigh is 2.5 ten thousand -3 ten thousand.Copolymer emulsion is applied by coating processes
Cloth can effectively reduce the surface tension of base material on various base materials, and assign base material excellent surface and interface performance, on low surface
The fields such as energy boundary material, low air-permeable surface material, low transparent liquid surfacing, which possess, to be widely applied.
Reaction temperature is low in the inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion preparation process of the present invention, former
Expect that waste discharge is few, price is low and with excellent film forming and surface and interface performance, with inexpensive, low temperature, environmental protection
Advantage.Compared with existing synthetic technology, the present invention has the advantage that：
1st, metal salt is slowly hydrolyzed in microemulsion phase, forms inorganic nanometer oxide material, assigns inorganic nanometer oxide material
Excellent surface polyhydroxy performance, thus be more beneficial for subsequently it is modified and synthetic polymer film forming surface and interface performance；
2nd, organic compound modified inorganic nano material, makes inorganic nano material turn into a part for polymer segment, than addition
Property nano material there is more excellent structural stability, while the addition of nano material in the polymer can be improved, Ke Yigao
Up to 30%；
3rd, the introducing of unsaturated polyether class, using the excellent lower temperature resistance of unsaturated polyether, can effectively solve polymer
Lower temperature resistance is poor, the defect such as film forming is crisp；
4th, the low-surface-energy design of film, can assign film has the effect of defoamer.
Embodiment
Technical scheme is described further below by embodiment.
Embodiment 1
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 61g sodium metasilicate, 123g ethyl acetate and 68g water, are weighed, is added in reactor, 90 DEG C of temperature is maintained, very
Reciprocal of duty cycle -0.06MPa, is stirred vigorously (rotating speed 150r/min) reaction 5h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 2h, obtain nano silicon；
(2) nano silicon 61g and acrylic acid 137g, are weighed, maintenance system temperature is 130 DEG C, vacuum-
0.05MPa, 3h is reacted under the conditions of heating reduced-pressure backflow, then is warming up to 150 DEG C, and vacuum is -0.08MPa, reacts 5h,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 1h, that is, obtain acrylic acid modified nano silicon；
(3) 5g modified Nanos particle, 1g azodiisobutyronitriles, 40g 1,2- dichloroethylene, 5g trichloro ethylenes, 10g, are weighed
Methyl methacrylate, 3g PEG-4000s and 10g dodecyl sodium sulfates, the monooctyl ester of 3g phosphorous acid three, 60g water, dimension
System temperature is held for 65 DEG C, 6h is reacted under nitrogen protection, that is, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-poly-
Ether copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 10min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, investigates film tension, whether transparent, transparent rate (being shown in Table 1), and this film has the excellent transparency and surface and interface performance.
Embodiment 2
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 50g sodium metasilicate, 113g ethyl acetate and 78g water, are weighed, is added in reactor, 80 DEG C of temperature is maintained, very
Reciprocal of duty cycle -0.07MPa, is stirred vigorously (rotating speed 160r/min) reaction 6h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
70 DEG C of dry 3h, obtain nano silicon；
(2) nano silicon 51g and acrylic acid 117g, are weighed, maintenance system temperature is 120 DEG C, vacuum-
0.07MPa, reacts 4h, then is warming up to 160 DEG C, and vacuum is -0.06MPa, and 6h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 75 DEG C of dry 2h, that is, obtain acrylic acid modified nano silicon；
(3), weigh 6g modified Nanos particle, 1.5g azodiisobutyronitriles, 45g 1,1- dichloroethylene, 5.5g trichloro ethylenes,
11g methyl methacrylates, 4g PEG-4000s and 7g neopelexes, 1g tetraethyl orthosilicates, 3g phosphorous acid
Triphenylmethyl methacrylate, 65g water, maintenance system temperature are 75 DEG C, and 5h is reacted under nitrogen protection, that is, obtains inorganic modified vinyl chloride-the third
Vinyl derivative copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 9min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 3
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 41g sodium metasilicate, 93g ethyl acetate and 78g water, are weighed to be added in reactor, temperature 60 C, vacuum is maintained
Degree -0.08MPa, is stirred vigorously (rotating speed 140r/min) reaction 8h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 8h, obtain nano silicon；
(2) nano silicon 71g and acrylic acid 167g, are weighed, maintenance system temperature is 145 DEG C, vacuum-
0.06MPa, reacts 4h, then is warming up to 160 DEG C, and vacuum is -0.08MPa, and 3h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 3h, that is, obtain acrylic acid modified nano silicon；
(3) 7g modified Nanos particle, 2g azodiisobutyronitriles, 50g 1,2- dichloroethylene, 6g trichloro ethylenes, 12g, are weighed
Methyl methacrylate, 5g PEG-4000s and 12g polyvinyl alcohol 217,2g phosphorous acid, 70g water, maintenance system temperature
For 65 DEG C, 6.5h is reacted under nitrogen protection, that is, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 8min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 4
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 71g sodium metasilicate, 163g ethyl acetate and 88g water, are weighed to be added in reactor, 80 DEG C of temperature, vacuum is maintained
Degree -0.07MPa, is stirred vigorously (rotating speed 155r/min) reaction 7h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 7h, obtain nano silicon；
(2) nano silicon 36g and acrylic acid 177g, are weighed, maintenance system temperature is 120 DEG C, vacuum-
0.06MPa, reacts 5h, then is warming up to 175 DEG C, and vacuum is -0.04MPa, and 4h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 6h, that is, obtain acrylic acid modified nano silicon；
(3), weigh 8g modified Nanos particle, 2.5g azodiisobutyronitriles, 55g vinylidene chlorides, 6.5g trichloro ethylenes,
13g methyl methacrylates, 6g PEG-4000s and the monooctyl ester of 9g OP-10,4g phosphorous acid three, 75g water, maintenance system
Temperature is 65 DEG C, and 4.5h is reacted under nitrogen protection, that is, obtains machine nano modification vinyl chloride-propylene analog derivative-polyethers copolymerization
Thing emulsion.
Inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion is coated with by brush coating process under 15 DEG C of environment of winter
On a glass, in 80 DEG C of dry 7min, machine nano modification vinyl chloride-propylene analog derivative-copolyether film is obtained, this
Film has the excellent transparency and surface and interface performance.
Embodiment 5
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 65g sodium metasilicate, 143g ethyl acetate and 98g water, are weighed to be added in reactor, temperature 70 C, vacuum is maintained
Degree -0.09MPa, is stirred vigorously (rotating speed 180r/min) reaction 2h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 6h, obtain nano silicon；
(2) nano silicon 57g and acrylic acid 146g, are weighed, maintenance system temperature is 136 DEG C, vacuum-
0.06MPa, reacts 4h, then is warming up to 170 DEG C, and vacuum is -0.09MPa, and 1h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 6h, that is, obtain acrylic acid modified nano silicon；
(3) 9g modified Nanos particle, 3g azodiisobutyronitriles, 60g 1,2-dichloroethenes, 7g trichloro ethylenes, 14g, are weighed
Methyl methacrylate, 7g PEG-4000s and 6g polyvinyl alcohol 217,3g neopelexes, 2g phosphorous acid three
Butyl ester, 55g water, maintenance system temperature are 65 DEG C, and 5.5h is reacted under nitrogen protection, that is, obtains inorganic modified vinyl chloride-the third
Vinyl derivative copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 6min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 6
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 0.001kg sodium metasilicate, 99.99kg ethyl acetate and 99.99kg water, are weighed to be added in reactor, temperature is maintained
80 DEG C, vacuum -0.09MPa is stirred vigorously (rotating speed 180r/min) reaction 2h under the conditions of heating reduced-pressure backflow；By
Filter, the washing of 500mL ethanol, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL washings
Wash, filter, 80 DEG C of dry 6h, obtain nano silicon；
(2) nano silicon 0.001kg and acrylic acid 0.001kg, are weighed, maintenance system temperature is 143 DEG C, vacuum-
0.06MPa, reacts 4.5h, then is warming up to 160 DEG C, and vacuum is -0.09MPa, is reacted under the conditions of heating reduced-pressure backflow
2h, after product is cooled to room temperature, through the washing of ethanol twice (each 500mL), filtering, twice water washing it is (each
500mL), filtering, 80 DEG C of dry 6h, that is, obtain acrylic acid modified nano silicon；
(3) 0.001g modified Nanos particle, 5g azodiisobutyronitriles, 0.0008g 1,2-dichloroethenes, 0.0002g tri-, are weighed
Vinyl chloride, 30g methyl methacrylates, 0.003g PEG-4000s and 14g polyvinyl alcohol 217,0.003g dodecyls
Benzene sulfonic acid sodium salt, 0.004g tributyl phosphites, 0.001g water, maintenance system temperature are 60 DEG C, and 6 are reacted under nitrogen protection
H, that is, obtain inorganic modified vinyl chloride-propylene analog derivative copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 6min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 7
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 50g sodium metasilicate, 60g ethyl acetate and 99.99g water, are weighed to be added in reactor, temperature 70 C is maintained, very
Reciprocal of duty cycle -0.09MPa, is stirred vigorously (rotating speed 180r/min) reaction 2h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 6h, obtain nano silicon；
(2) nano silicon 30g and acrylic acid 99.99g, are weighed, maintenance system temperature is 135 DEG C, vacuum-
0.07MPa, reacts 4h, then is warming up to 170 DEG C, and vacuum is -0.09MPa, and 1h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 6h, that is, obtain acrylic acid modified nano silicon；
(3) 30g modified Nanos particle, 0.001g azodiisobutyronitriles, 86.99g 1,2-dichloroethenes, 13g trichlorines, are weighed
Ethene, 0.001g methyl methacrylates, 7g PEG-4000s and 0.001g polyvinyl alcohol 217,5g detergent alkylate sulphurs
Sour sodium, 3g tributyl phosphites, 99.99g water, maintenance system temperature are 65 DEG C, and 4.5h is reacted under nitrogen protection, is produced
To inorganic modified vinyl chloride-propylene analog derivative copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 6min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 8
A kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 69g sodium metasilicate, 153g ethyl acetate and 99g water, are weighed to be added in reactor, 75 DEG C of temperature, vacuum is maintained
Degree -0.08MPa, is stirred vigorously (rotating speed 180r/min) reaction 2h under the conditions of heating reduced-pressure backflow；Through filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 6h, obtain nano silicon；
(2) nano silicon 67g and acrylic acid 143g, are weighed, maintenance system temperature is 138 DEG C, vacuum-
0.06MPa, reacts 6h, then is warming up to 172 DEG C, and vacuum is -0.09MPa, and 2h is reacted under the conditions of heating reduced-pressure backflow,
After product is cooled to room temperature, through the washing of ethanol twice (each 500mL), twice filtering, water washing (each 500mL), mistake
Filter, 80 DEG C of dry 6h, that is, obtain acrylic acid modified nano silicon；
(3), weigh 20g modified Nanos particle, 2g dibenzoyl peroxides, 25g 1,2-dichloroethenes, 2g trichloro ethylenes,
7g polyethylene glycol -600,6g stearic acid, 13g methyl methacrylates and 3g OP-10,2
G phosphorous acid, 40g water, under nitrogen protection, maintenance system temperature react to be stirred vigorously (rotating speed 200r/min) at 50 DEG C
After 0.5h, remaining 180g modified Nanos particle is at the uniform velocity added in reactor in 2h；And maintenance system temperature is 63 DEG C
Lower reaction 5h, that is, obtain inorganic modified vinyl chloride-propylene analog derivative-polyethers copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion passes through brush coating process
Coating on a glass, in 80 DEG C of dry 6min, obtains inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether
Film, this film has the excellent transparency and surface and interface performance.
Embodiment 9
A kind of inorganic nano vinyl chloride-propylene analog derivative-copolyether emulsion, its preparation method comprises the following steps：
(1) 61g sodium metasilicate, 123g ethyl acetate and 68g water, are weighed, is added in reactor, 90 DEG C of temperature is maintained, very
Reciprocal of duty cycle -0.06MPa, is stirred vigorously (rotating speed 150r/min) reaction 5h under the conditions of heating reduced-pressure backflow；Filtering, 500mL
Ethanol washing, filtering, 500mL water washings, filtering, the washing of 500mL ethanol, filtering, 500mL water washings, filtering,
80 DEG C of dry 2h, obtain nano silicon；
(2) 5g nano silicons, 1g azodiisobutyronitriles, 40g 1,2- dichloroethylene, 5g trichloro ethylenes, 10g, are weighed
Methyl methacrylate, 3g PEG-4000s and 10g dodecyl sodium sulfates, the monooctyl ester of 3g phosphorous acid three, 60g water, dimension
System temperature is held for 65 DEG C, 6h is reacted under nitrogen protection, that is, obtains inorganic nano vinyl chloride-propylene analog derivative-polyethers common
Copolymer emulsion.
Under 15 DEG C of environment of winter, inorganic nano vinyl chloride-propylene analog derivative-copolyether emulsion is coated with by brush coating process
On a glass, in 80 DEG C of dry 10min, inorganic nano vinyl chloride-propylene analog derivative-copolyether film is obtained, is investigated
Film tension, whether transparent, transparent rate.
The performance parameter of copolymer emulsion and its film made from the embodiment 1-6 of table 1
Note：1. the PVDC emulsions that control synthesizes for Zhejiang Juhua Co., Ltd.；
2. surface tension is determined by contact angle tester；
3. transparent rate is performed according to GB：The measure of GB/T 2410-2008 transparent plastics light transmittances and mist degree；
4. this test is carried out under conditions of relatively harsh：15 DEG C of winter；
5. silica mass ratio in modified Nano particle is 45%；
As shown in Table 1, metal salt is slowly hydrolyzed in microemulsion phase by the inventive method, forms inorganic nano material, assigned
The excellent surface polyhydroxy performance of inorganic nanometer oxide material, thus be more beneficial for subsequently it is modified and synthetic polymer into
The surface and interface performance of film；Organic compound modified inorganic nano material, makes inorganic nano material turn into one of polymer segment
Point, there is more excellent structural stability than addition property nano material, while the addition of nano material in the polymer can be improved
Amount, can be up to 30%；And compare and can only at most be added to 10%, that is, there is emulsion breaking, performance drastically declines；Insatiable hunger
With the introducing of polyethers, using the excellent lower temperature resistance of unsaturated polyether, the lower temperature resistance that can effectively solve polymer is poor,
The defect such as film forming is crisp；Inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion system made from embodiment 1-8
The film obtained has the excellent transparency and surface and interface performance, and film tension is 30~60 × 10-3Between N/m.And embodiment 9
In inorganic nano material is modified due to no use organic matter, directly affects the transparent performance after film forming, also reduce
The addition of nano material in the polymer.
Claims (10)
1. a kind of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion, it is characterised in that including following original
Expect component：Modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water, it is described
Modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, the mass ratio of auxiliary agent and water are
0.001~30：0.001~5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~99.99；Its
In, described modified Nano particle is reacted by inorganic nano-particle and unsaturated acids to be made, described inorganic nano-particle and insatiable hunger
Mass ratio with acid is 0.001~30：0.001~99.99；Described inorganic nano-particle is made by metal salt and ester reaction,
Described metal salt and the mass ratio of esters are 0.001~50：0.001~99.99.
2. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 1, it is special
Levy is that described coating is by following preparation method with inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion
It is obtained：(1) it is, 0.001~50 according to mass ratio by metal salt, esters and water：0.001~99.99：0.001~99.99 adds
Enter into reactor, stir, 50~160 DEG C of maintenance system temperature, vacuum -0.01~-0.1MPa, in heating reduced-pressure backflow
Under the conditions of react 2~30h, product through filtering, washing, dry, obtain inorganic nano-particle；(2), inorganic nano-particle and
Unsaturated acids is according to mass ratio 0.001~30：0.001~99.99 in 80~180 DEG C of temperature, vacuum -0.01~-0.1MPa,
2~30h of reaction under the conditions of reduced-pressure backflow is heated, product washs, dried, that is, obtain modified Nano particle through filtering；(3)、
Modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water are according to mass ratio
0.001~30：0.001~5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~99.99,
20~100 DEG C of temperature, nitrogen protection 0.1~20h of lower reaction, that is, obtain inorganic nanometer modified vinyl chloride -- and propylene analog derivative-
Copolyether emulsion.
3. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 1 or 2,
It is characterized in that the mass ratio of described metal salt, esters and water is 1~2：1~10：1~5；Described inorganic nano-particle
Mass ratio with unsaturated acids is 1~30：1~75；Described modified Nano particle, initiator, vinyl chloride, propylene class are spread out
Biology, unsaturated ether, the mass ratio of auxiliary agent and water are 1~30：1~5：1~90：1~30：1~15：1~15：
1~90.
4. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 3, it is special
Levy is that the mass ratio of described metal salt, esters and water is 1：2~2.5：1~2；Described inorganic nano-particle and insatiable hunger
Mass ratio with acid is 1：2~5；Described modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturation
The mass ratio of ethers, auxiliary agent and water is 1：0.2~0.35：7~9：1.5~2：0.6~0.8：1~3：6~12.
5. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 1 or 2,
It is characterized in that the described temperature for preparing inorganic nano-particle is 60~90 DEG C, vacuum is -0.06~-0.09MPa, reaction
Time is 2~8h；The described temperature for preparing modified Nano particle be 120~175 DEG C, vacuum be -0.04~-
0.09MPa, the reaction time is 5~10h；Described prepares inorganic nanometer modified vinyl chloride -- propylene analog derivative-copolyether
The temperature of emulsion is 50~75 DEG C, and the reaction time is 4.5~7.5h.
6. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 1 or 2, its
It is one in silicon salt, titanium salt, calcium salt, magnesium salts, aluminium salt, boron salt, pink salt, zinc salt, barium salt to be characterised by described metal salt
Plant or several mixtures；
Described esters are methyl formate, Ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, acetic acid
Propyl ester, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyric acid
One or more of mixtures of propyl ester, butyl butyrate；
Described unsaturated acids is acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylate, butenoic acid, methyl butene
Acid, one or more of mixtures of ethyl butenoic acid, propyl group butenoic acid；
Described initiator is azo-initiator, peroxide initiator, redox initiator, the preferably isobutyl of azo two
Nitrile, peroxidating two acyl, persulfate, dibenzoyl peroxide, persulfate-acid sulfite or DMA
One or more of mixtures；
Described vinyl chloride is one or more of mixing of vinyl chloride, 1,1- dichloroethylene, 1,2- dichloroethylene, trichloro ethylene
Thing；
The propylene analog derivative is acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylate, methyl acrylate, first
Base methyl acrylate, ethyl methyl acrylate, propylacrylate methyl esters, ethyl acrylate, EMA, ethyl third
Olefin(e) acid ethyl ester, propylacrylate ethyl ester, propyl acrylate, propyl methacrylate, ethyl propylene propyl propionate, propylacrylate
Propyl ester, acrylamide, Methacrylamide, ethyl acrylamide, propylacrylamide, acrylonitrile, methacrylonitrile, second
One or more of mixtures of base acrylonitrile, propyl group acrylonitrile；
The unsaturated polyether class is polyethylene glycol, one or more of mixtures of PolyTHF.
7. the preparation side of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion described in claim 1
Method, it is characterised in that comprise the following steps：
(1) it is, 0.001~50 according to mass ratio by metal salt, esters and water：0.001~99.99：0.001~99.99 is added to
In reactor, stirring, 50~160 DEG C of maintenance system temperature, vacuum -0.01~-0.1MPa, in heating reduced-pressure backflow condition
2~30h of lower reaction, product obtains inorganic nano-particle through filtering, washing, dry；
(2), inorganic nano-particle and unsaturated acids are according to mass ratio 0.001~30：0.001~99.99 temperature 80~
180 DEG C, heating reduced-pressure backflow reacts 2~30h under the conditions of vacuum -0.01~-0.1MPa, product is washing, dry through filtering
It is dry, that is, obtain modified Nano particle；
(3), modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, auxiliary agent and water are according to matter
Measure ratio 0.001~30：0.001~5：0.001~99.99：0.001~30：0.001~15：0.001~15：0.001~
99.99, in 20~100 DEG C of temperature, nitrogen protection 0.1~20h of lower reaction obtains inorganic nanometer modified vinyl chloride -- propylene
Analog derivative-copolyether emulsion.
8. the preparation of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 7
Method, it is characterised in that in step (1), the mass ratio of described metal salt, esters and water is 1~2：1~10：1~5, it is excellent
Elect 1 as：2~2.5：1~2；
In step (2), described inorganic nano-particle and the mass ratio of unsaturated acids are 1~30：1~75, preferably 1：2~
5；
In step (3), described modified Nano particle, initiator, vinyl chloride, propylene analog derivative, unsaturated ether, help
The mass ratio of agent and water is 1~30：1~5：1~90：1~30：1~15：1~15：1~90, preferably 1：0.2~
0.35：7~9：1.5~2：0.6~0.8：1~3：6~12.
9. the preparation of inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion according to claim 7
Method, it is characterised in that in step (1), the described temperature for preparing inorganic nano-particle is 60~90 DEG C, vacuum for-
0.06~-0.09MPa, the reaction time is 2~8h；
In step (2), the described temperature for preparing modified Nano particle is 120~175 DEG C, vacuum is -0.04~-
0.09MPa, the reaction time is preferably 5~10h；
In step (3), described prepares inorganic nanometer modified vinyl chloride -- and the temperature of propylene analog derivative-copolyether emulsion is
50~75 DEG C, the reaction time is 4.5~7.5h.
10. inorganic nanometer modified vinyl chloride-propylene analog derivative-copolyether emulsion coating described in claim 1 is in base material
Surface prepares the application of hydrophobic membrane or automatically cleaning film.
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| CN1369511A (en) * | 2001-02-12 | 2002-09-18 | 上海绿纳化工材料技术有限公司 | Process for preparing hybridized substance with core-shell structre from organic high-molecular material and nano inorganic material |
| CN1618866A (en) * | 2004-10-11 | 2005-05-25 | 华东理工大学 | Preparation method of polyvinyl chloride/inorganic rigid particle composite resin |
| WO2012175431A2 (en) * | 2011-06-20 | 2012-12-27 | Bayer Intellectual Property Gmbh | Production of films having flexible barrier coatings containing phyllosilicates |
| CN105037646A (en) * | 2015-07-17 | 2015-11-11 | 清华大学 | Polymer nano / micro particle additive and preparation method thereof |
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| CN101186666A (en) * | 2007-11-19 | 2008-05-28 | 上海氯碱化工股份有限公司 | Method for preparing polyvinylidene chloride and acrylic ester copolymerization latex |
| CN101475672B (en) * | 2009-01-14 | 2012-01-18 | 河南大学 | Method for modifying polychloroethylene by in-situ polymerization of nano silicon dioxide |
| CN105085761A (en) * | 2015-08-14 | 2015-11-25 | 湖州新奥利吸附材料有限公司 | Preparation method of PVDC composition for carbon molecular sieve |
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| CN1369511A (en) * | 2001-02-12 | 2002-09-18 | 上海绿纳化工材料技术有限公司 | Process for preparing hybridized substance with core-shell structre from organic high-molecular material and nano inorganic material |
| CN1618866A (en) * | 2004-10-11 | 2005-05-25 | 华东理工大学 | Preparation method of polyvinyl chloride/inorganic rigid particle composite resin |
| WO2012175431A2 (en) * | 2011-06-20 | 2012-12-27 | Bayer Intellectual Property Gmbh | Production of films having flexible barrier coatings containing phyllosilicates |
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