CN110105490A - Preparation and application containing reactive Ti-Si sol and its modification (methyl) acrylic ester polymerization lotion - Google Patents
Preparation and application containing reactive Ti-Si sol and its modification (methyl) acrylic ester polymerization lotion Download PDFInfo
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- CN110105490A CN110105490A CN201910481119.8A CN201910481119A CN110105490A CN 110105490 A CN110105490 A CN 110105490A CN 201910481119 A CN201910481119 A CN 201910481119A CN 110105490 A CN110105490 A CN 110105490A
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Abstract
The preparation and application containing reactive Ti-Si sol and its modification (methyl) acrylic ester polymerization lotion that the invention discloses a kind of.The present invention has been prepared by sol-gel method containing reactive Ti-Si sol, the organic siloxane modified nano-TiO of this method2, while mercaptosilane coupling agents are further introduced into, a kind of Ti-Si sol containing reactivity is obtained, polymerization reaction is can be directly used for, simplifies technique, and solve nano-TiO2Reunion is led to the problem of in preparation and application process.Polymerization reaction also is used for containing reactive Ti-Si sol by obtained in the present invention, select suitable (methyl) acrylate monomer, water, anion emulsifier, nonionic emulsifier, acrylic acid and initiator hybrid reaction, it obtains containing modified (methyl) the acrylic ester polymerization lotion of reactive Ti-Si sol, gained emulsion property is stablized, in terms of can be applied to coating, leather, adhesive, papermaking and fabric finishing agent.
Description
Technical field
It is the invention belongs to acrylic acid ester emulsion preparation field, in particular to a kind of containing reactive Ti-Si sol and its modification
The preparation and application of (methyl) acrylic ester polymerization lotion.
Background technique
Poly- (methyl) acrylic acid ester emulsion has many advantages, such as environmentally friendly, at low cost and good film-forming property, and its film flexibility, resistance to
Time property and adhesive force are excellent, are widely used in the industries such as coating, leather, adhesive, papermaking and fabric finishing agent.But due to
Poor processability, cold resistance is poor, not acid and alkali-resistance, the disadvantages of hardening and wearing no resistance at room temperature, limits it to a certain extent
Using.Common method of modifying has polyurethane-modified, silicon/fluorine modified, crosslinking curing modified and inorganic nano particle modified etc..
Currently, there are mainly two types of methods for inorganic nano particle modified polyacrylate dispersion: physical blending and in-situ polymerization,
The purpose is to have many advantages, such as good heat resistance, chemical stability and high hardness using inorganic particulate, in conjunction with it is inorganic with have
The compound advantage of machine, improves the performance of latex film, expands its application field.Common modified particle mainly has silica
(SiO2), titanium dioxide (TiO2), montmorillonite and zinc oxide (ZnO) etc..Wherein, nano-TiO2In addition to having small-size effect, table
Outside the shared characteristic of the inorganic nano-particles such as face interfacial effect and quantum size effect, reaches antibacterial there are also absorbable ultraviolet light and kill
The effect of bacterium, and the against weather of polyacrylate dispersion and the cohesive force of ageing resistance and its glue film can be improved.But
Due to nano-TiO2The large specific surface area of particle, surface can be high, the poor compatibility with (methyl) acrylate polymer, Yi Fasheng
Reunite, brings larger difficulty for its practical application.
Therefore, nano-TiO is improved2The chemical bonds and dispersibility of particle and (methyl) acrylate polymer, become
Prepare the critical issue with poly- (methyl) acrylic acid ester emulsion of modification of good stability and service performance.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of molten containing reactive titanium silicon
Glue.
Another object of the present invention is to provide the preparation methods containing reactive Ti-Si sol.
Another object of the present invention is to provide the Ti-Si sol containing reactivity to prepare modified (methyl) acrylate
Application in polymerized emulsion.
A further object of the present invention is to provide one kind containing modified (methyl) acrylic ester polymerization cream of reactive Ti-Si sol
Liquid.
The purpose of the invention is achieved by the following technical solution: for one kind containing reactive Ti-Si sol, described contains reactivity
Ti-Si sol has structure shown in formula I:
Preparation method of the colloidal sol containing reactive Ti-Si sol, includes the following steps:
Will 2~30 parts by weight titanate esters and 20~80 parts by weight dehydrated alcohols mix after be heated to 20~65 DEG C, then plus
Enter 0.3~10 part by weight of catalyst and 1~5 parts by weight water, at 20~65 DEG C react 5~for 24 hours, add 5~15 parts by weight
Organosiloxane reacts 5~20h at 35~65 DEG C, obtains modified Nano TiO2Colloidal sol；Finally by 4~25 parts by weight sulfydryls
Silane coupling agent is added to modified Nano TiO2In colloidal sol, 6~30h is reacted at 30~70 DEG C, is obtained molten containing reactive titanium silicon
Glue.
The titanate esters are one or more of isopropyl titanate, butyl titanate and tetraethyl titanate.
The catalyst be nitric acid solution, sulfuric acid solution, hydrochloric acid solution, acetum, ammonium hydroxide, sodium hydroxide solution and
One or more of potassium hydroxide solution.
The hydrochloric acid solution is preferably the hydrochloric acid solution of mass fraction 37%.
The ammonium hydroxide is preferably the ammonium hydroxide of mass fraction 25~28%.
The nitric acid solution is preferably the nitric acid solution of mass fraction 65~68%.
The acetum is preferably the acetum of mass fraction 99.5%.
The organosiloxane is methyltrimethoxysilane, methyltriethoxysilane, dimethylformamide dimethyl oxygroup silicon
One or more of alkane and dimethyl diethoxysilane.
The mercaptosilane coupling agents are one of mercaptopropyl trimethoxysilane and mercaptopropyltriethoxysilane
Or two kinds.
The application containing reactive Ti-Si sol in modified poly- (methyl) acrylic acid ester emulsion of preparation.
One kind having the structure as shown in Formula II containing modified (methyl) the acrylic ester polymerization lotion of reactive Ti-Si sol:
Wherein, R1、R2、R4And R5It is hydrogen or methyl；R3And R6The saturated alkane for being 1~10 for carbon number；n1-n4It is 4~2000
The interior natural number that can be divided exactly by 4.
The preparation method of described modified (methyl) the acrylic ester polymerization lotion containing reactive Ti-Si sol, including walk as follows
It is rapid:
By 75~100 parts by weight water, 4~9 parts by weight anion emulsifiers, 3~5 parts by weight nonionic emulsifiers mix and
0.5~2 parts by weight of acrylic acid is uniformly mixed, and 15~50 parts by weight (methyl) acrylate is then added under nitrogen protection
Monomer and 3~8 parts by weight are above-mentioned containing reactive Ti-Si sol, quickly stir 0.5~3h and carry out pre-emulsification, add 0.3~3.0
Parts by weight initiator, 60~90 DEG C of 4~12h of reaction are obtained containing modified (methyl) acrylic ester polymerization cream of reactive Ti-Si sol
Liquid.
The anion emulsifier is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, ten
One or more of six alkyl benzene sulphonates and octadecyl benzenesulfonic acid.
The nonionic emulsifier is polyoxyethylene sorbitan monostearate, polyoxyethylene alkyl ether and alkyl phenol
One or more of polyoxyethylene ether.
The acrylic acid is one or both of acrylic acid and methacrylic acid.
(methyl) acrylate monomer is methyl acrylate, ethyl acrylate, n-propyl, acrylic acid fourth
Ester, methyl methacrylate, ethyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid
One or more of different monooctyl ester and glycidyl methacrylate.
The initiator is one or both of ammonium persulfate and potassium peroxydisulfate.
The reactive Ti-Si sol and/or modified (methyl) acrylate containing reactive Ti-Si sol are poly-
Close application of the lotion in coating, leather, adhesive, papermaking and fabric finishing agent.
The present invention has the following advantages and effects with respect to the prior art:
1, the present invention has been prepared by sol-gel method containing reactive Ti-Si sol, this method organosiloxane
Modified Nano TiO2, while mercaptosilane coupling agents are further introduced into, a kind of Ti-Si sol containing reactivity is obtained, can be directly used for
Polymerization reaction simplifies technique, and solves nano-TiO2Reunion is led to the problem of in preparation and application process.
2, under nitrogen protection of the present invention, select suitable (methyl) acrylate monomer, water, anion emulsifier, it is non-from
Sub- emulsifier, acrylic acid, Ti-Si sol, initiator hybrid reaction containing reactivity are obtained containing the modified (first of reactive Ti-Si sol
Base) acrylic ester polymerization lotion.Gained emulsion property is stablized, and film has excellent heat resistance (resistant of high or low temperature), resistance to
The performances such as time property and antibiotic and sterilizing.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.Unless
It illustrates, agents useful for same and raw material of the present invention can pass through commercially available acquisition.
Embodiment 1
The preparation method of one kind modified (methyl) acrylic ester polymerization lotion containing reactive Ti-Si sol, including following step
It is rapid:
(1) preparation containing reactive Ti-Si sol
Three-necked flask equipped with thermometer, condenser pipe and blender is put into the metatitanic acid four that 15 parts by weight are added in reactor
Butyl ester and 70 parts by weight dehydrated alcohols, are heated to 50 DEG C, add 0.5 parts by weight hydrochloric acid solution (mass fraction 37%), 2 parts are gone
Ionized water reacts 5h at 50 DEG C, obtains the titanium colloidal sol that solid content is 4%.It then proceedes to that 7 parts by weight methyl trimethoxy oxygroups are added
Silane reacts 8h at 35 DEG C, obtains modified Nano TiO2Colloidal sol.It is further continued for that 5 parts by weight mercaptopropyl trimethoxysilanes are added,
45 DEG C of reaction 6h are obtained containing reactive Ti-Si sol (15wt%).
(2) preparation of modified (methyl) acrylic acid ester emulsion containing reactive Ti-Si sol
85 parts by weight water, 5 weights are added in the reaction vessel equipped with blender, thermometer, condenser pipe and nitrogen access tube
Part neopelex, 4 parts by weight of polyoxyethylene alkyl ethers are measured, the acrylic acid of 1 parts by weight stirs evenly, and protects in nitrogen
Lower 45 parts by weight of acrylic acid methyl esters, the 2 parts by weight steps (1) of being added of shield are resulting containing reactive Ti-Si sol (15wt%), quickly
0.5h pre-emulsification is stirred, 0.8 parts by weight potassium peroxydisulfate is then added, 75 DEG C of reaction 5h are removed under reduced pressure ethyl alcohol, obtain modified propylene
Sour methyl esters polymerized emulsion.
(3) emulsion property
Emulsion solid content: 39.4wt%；Emulsion particle diameter: 268nm；Lotion places stationary phase (room temperature, sealing): 8 months.
Embodiment 2
The preparation method of one kind modified (methyl) acrylic ester polymerization lotion containing reactive Ti-Si sol, including following step
It is rapid:
(1) preparation containing reactive Ti-Si sol
Three-necked flask equipped with thermometer, condenser pipe and blender is put into reactor, the metatitanic acid of 10 parts by weight is added
Isopropyl ester and 60 parts by weight dehydrated alcohols, are heated to 40 DEG C, add 1.8 parts by weight ammonium hydroxide (mass concentration is 25~28%), 4
Parts by weight of deionized water reacts 6h at 40 DEG C, obtains the titanium colloidal sol that solid content is 3.7%.It then proceedes to that 10 parts by weight are added
Dimethyldimethoxysil,ne reacts 8h at 55 DEG C, obtains modified Nano TiO2Colloidal sol.It is further continued for that 5 parts by weight mercaptos third are added
Base trimethoxy silane reacts 6h at 50 DEG C, obtains containing reactive Ti-Si sol (19.6wt%).
(2) preparation of modified (methyl) acrylic acid ester emulsion containing reactive Ti-Si sol
90 parts by weight water, 2 weights are added in the reaction vessel equipped with blender, thermometer, condenser pipe and nitrogen access tube
Measure part neopelex and 3 parts by weight lauryl sodium sulfate, 5 parts by weight alkylphenol-polyethenoxy base ethers, 0.5 weight
The methacrylic acid of part, stirs evenly, 20 weight parts of methacrylic acid N-butyls and 10 parts by weight third is added under nitrogen protection
E pioic acid methyl ester, 10 parts by weight steps (1) are resulting containing reactive Ti-Si sol (19.6wt%), quickly stir 1h pre-emulsification, so
After 1 parts by weight potassium peroxydisulfate is added, ethyl alcohol is removed under reduced pressure in 75 DEG C of reaction 9h, obtains containing reactive Ti-Si sol modified methyl third
Olefin(e) acid N-butyl polymerized emulsion.
(3) emulsion property
Emulsion solid content: 32.3wt%, emulsion particle diameter: 335nm, lotion place stationary phase (room temperature, sealing): 7 months.
Embodiment 3
One kind is containing modified (methyl) the acrylic ester polymerization lotion of reactive Ti-Si sol and preparation method, including following step
It is rapid:
(1) preparation containing reactive Ti-Si sol
Three-necked flask equipped with thermometer, condenser pipe and blender is put into reactor, the metatitanic acid of 20 parts by weight is added
Isopropyl ester and 80 parts by weight dehydrated alcohols, are heated to 65 DEG C, add 1.5 parts by weight nitric acid solutions (mass concentration be 65~
68%) and the acetic acid of 0.5 parts by weight, 3 parts by weight of deionized water react 20h at 65 DEG C, obtain the titanium that solid content is 5.3%
Colloidal sol.It then proceedes to that 4 parts by weight methyltriethoxysilane and 8 parts by weight of dimethyldimethoxysil,ne are added, at 35 DEG C
8h is reacted, modified Nano TiO is obtained2Colloidal sol.It is further continued for that 10 parts by weight mercaptopropyl trimethoxysilanes are added, is reacted at 40 DEG C
20h is obtained containing reactive Ti-Si sol (21.7wt%).
(2) preparation of modified (methyl) acrylic acid ester emulsion containing reactive Ti-Si sol
85 parts by weight water, 6 weights are added in the reaction vessel equipped with blender, thermometer, condenser pipe and nitrogen access tube
Part cetyl benzenesulfonic acid, 6 parts by weight of polyoxyethylene alkyl ethers are measured, the acrylic acid of 0.5 parts by weight stirs evenly, and protects in nitrogen
10 weight parts of methacrylic acid ethyl esters of the lower addition of shield, 10 weight parts of methacrylic acid N-butyls and 20 weight parts of methacrylic acid are different
Monooctyl ester, 8 parts by weight steps (1) are resulting containing reactive Ti-Si sol (21.7wt%), quickly stir 3h pre-emulsification, are then added
2 parts by weight potassium peroxydisulfates, 80 DEG C of reaction 8h, are removed under reduced pressure ethyl alcohol, obtain containing reactive Ti-Si sol modified methyl acrylic
Polymerized emulsion.
(3) emulsion property
Emulsion solid content: 39.8wt%, emulsion particle diameter: 415nm, lotion place stationary phase (room temperature, sealing): 8 months.
Embodiment 4
One kind is containing modified (methyl) the acrylic ester polymerization lotion of reactive Ti-Si sol and preparation method, including following step
It is rapid:
(1) preparation containing reactive Ti-Si sol
Three-necked flask equipped with thermometer, condenser pipe and blender is put into reactor, the metatitanic acid four of 2 parts by weight is added
Ethyl ester and 80 parts by weight dehydrated alcohols, are heated to 35 DEG C, add the acetum (mass concentration 99.5%) of 1 parts by weight, and 2
Parts by weight of deionized water reacts at 35 DEG C and obtains the titanium colloidal sol that solid content is 0.6% for 24 hours.It then proceedes to that 5 parts by weight are added
Methyltrimethoxysilane and 10 parts by weight dimethyl diethoxysilanes, react 12h at 40 DEG C, obtain modified Nano TiO2
Colloidal sol.It is further continued for that 10 parts by weight mercaptopropyl trimethoxysilanes are added, reacts 14h at 50 DEG C, obtain containing reactive Ti-Si sol
(23.2wt%).
(2) preparation of modified (methyl) acrylic acid ester emulsion containing reactive Ti-Si sol is equipped with blender, thermometer, cold
90 parts by weight water, 4 parts by weight octadecyl benzenesulfonic acids, 3 parts by weight polyoxies are added in the reaction vessel of solidifying pipe and nitrogen access tube
Ethylene sorbitan monostearate, the acrylic acid of 0.5 parts by weight, stirs evenly, and 2 parts by weight propylene are added under nitrogen protection
Acid butyl ester and 10 weight parts of methacrylic acid ethylene oxidic esters, 5 parts by weight steps (1) are resulting containing reactive Ti-Si sol
(23.2wt%) quickly stirs 2h pre-emulsification, 1 parts by weight ammonium persulfate is then added, and ethyl alcohol is removed under reduced pressure in 70 DEG C of reaction 6h,
It obtains containing reactive Ti-Si sol modified methyl acrylic polymerized emulsion.
(3) emulsion property
Emulsion solid content: 19.1wt%, emulsion particle diameter: 446nm, lotion place stationary phase (room temperature, sealing): 7 months.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. one kind is containing reactive Ti-Si sol, which is characterized in that described that there is knot shown in formula I containing reactive Ti-Si sol
Structure:
2. preparation method of the colloidal sol according to claim 1 containing reactive Ti-Si sol, which is characterized in that including walking as follows
It is rapid:
20~65 DEG C are heated to after 2~30 parts by weight titanate esters and 20~80 parts by weight dehydrated alcohols are mixed, is then added 0.3
~10 part by weight of catalyst and 1~5 parts by weight water, at 20~65 DEG C react 5~for 24 hours, add 5~15 parts by weight organosilicons
Oxygen alkane reacts 5~20h at 35~65 DEG C, obtains modified Nano TiO2Colloidal sol；It is finally that 4~25 parts by weight hydrosulphonyl silanes are even
Connection agent is added to modified Nano TiO2In colloidal sol, 6~30h is reacted at 30~70 DEG C, is obtained containing reactive Ti-Si sol.
3. preparation method of the colloidal sol according to claim 2 containing reactive Ti-Si sol, it is characterised in that:
The titanate esters are one or more of isopropyl titanate, butyl titanate and tetraethyl titanate；
The organosiloxane be methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysil,ne and
One or more of dimethyl diethoxysilane.
4. preparation method of the colloidal sol according to claim 2 containing reactive Ti-Si sol, it is characterised in that:
The catalyst is nitric acid solution, sulfuric acid solution, hydrochloric acid solution, acetum, ammonium hydroxide, sodium hydroxide solution and hydrogen-oxygen
Change one or more of potassium solution；
The mercaptosilane coupling agents are one of mercaptopropyl trimethoxysilane and mercaptopropyltriethoxysilane or two
Kind.
5. the application described in claim 1 containing reactive Ti-Si sol in modified poly- (methyl) acrylic acid ester emulsion of preparation.
6. one kind is containing modified (methyl) the acrylic ester polymerization lotion of reactive Ti-Si sol, which is characterized in that have such as Formula II institute
The structure shown:
Wherein, R1、R2、R4And R5It is hydrogen or methyl；R3And R6The saturated alkane for being 1~10 for carbon number；n1-n4For energy in 4~2000
The natural number divided exactly by 4.
7. the preparation method of modified (methyl) acrylic ester polymerization lotion as claimed in claim 6 containing reactive Ti-Si sol,
It is characterized in that, includes the following steps:
By 75~100 parts by weight water, 4~9 parts by weight anion emulsifiers, 3~5 parts by weight nonionic emulsifiers mixing and 0.5
~2 parts by weight of acrylic acid are uniformly mixed, and 15~50 parts by weight (methyl) acrylate list is then added under nitrogen protection
Body and 3~8 parts by weight are described in claim 1 containing reactive Ti-Si sol, quickly stir 0.5~3h and carry out pre-emulsification, then plus
Enter 0.3~3.0 parts by weight initiator, 60~90 DEG C of 4~12h of reaction are obtained containing modified (methyl) propylene of reactive Ti-Si sol
Acid esters polymerized emulsion.
8. the preparation side of modified (methyl) acrylic ester polymerization lotion according to claim 7 containing reactive Ti-Si sol
Method, it is characterised in that:
The acrylic acid is one or both of acrylic acid and methacrylic acid；
(methyl) acrylate monomer be methyl acrylate, ethyl acrylate, n-propyl, butyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid are different
One or more of monooctyl ester and glycidyl methacrylate.
9. the preparation side of modified (methyl) acrylic ester polymerization lotion according to claim 7 containing reactive Ti-Si sol
Method, it is characterised in that:
The anion emulsifier is lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, hexadecane
One or more of base benzene sulfonic acid and octadecyl benzenesulfonic acid；
The nonionic emulsifier is polyoxyethylene sorbitan monostearate, polyoxyethylene alkyl ether and alkyl phenol polyoxy
One or more of vinyl ethers；
The initiator is one or both of ammonium persulfate and potassium peroxydisulfate.
10. any one of reactivity Ti-Si sol described in claim 1 and/or claim 6 are modified containing reactive Ti-Si sol
Application of (methyl) the acrylic ester polymerization lotion in coating, leather, adhesive, papermaking and fabric finishing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910481119.8A CN110105490A (en) | 2019-06-04 | 2019-06-04 | Preparation and application containing reactive Ti-Si sol and its modification (methyl) acrylic ester polymerization lotion |
Applications Claiming Priority (1)
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