A kind of environment-friendly type aqueous rubber protective film and preparation method thereof
Technical field
The invention belongs to rubber chemistry technical field of modification, and in particular to a kind of environment-friendly type aqueous rubber protective film and its system
Preparation Method.
Background technology
Sheet metal after metal and coating is in follow-up processing and transportation, in order to prevent surface tear and dirt
Dye, all can paste layer protecting film on surface.Existing frequently-used diaphragm is that PE coats acrylic glue either solvent-borne type rubber
System.Acrylic glue cost is low, but the chemical characteristic due to material in itself, causes its viscosity unstable, bad adaptability, it is impossible to
Meet that diaphragm " good patch is easily torn " requires well.Solvent-borne type rubbery system it is viscosity stabilized, but bottom is done in production process
The adhesion improved with base material film is applied, and substantial amounts of organic solvent is used in process, production environment is poor, and may band
Carry out environmental pollution.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of environment-friendly type aqueous rubber protective film and preparation method thereof, institute
The environment-friendly type aqueous rubber protective film being prepared is viscosity stabilized, and releasable can be preferably.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion;
Macromole emulsifying agent 6-10 parts;
Butyl acrylate(BA)5-20 parts;
Isooctyl acrylate monomer(EHA)10-15 parts;
Methyl methacrylate(MMA)0-6 parts;
Acrylic acid(AA)0-2 parts;
Methacrylic acid(MAA)0-2 parts;
Ammonium persulfate 1-3 parts.
The macromole emulsifying agent is with butyl acrylate(BA)Or styrene(St)For hydrophobic monomer, methacrylic acid
(MAA)For water-soluble monomer, ammonium persulfate is initiator, and DNS-86 is reactive emulsifier, anti-by microemulsion polymerization method
It should be prepared.
In parts by weight, each component dosage of the macromole emulsifying agent is:Butyl acrylate(BA)Or styrene(St)
50-85 parts, methacrylic acid(MAA)15-50 parts, ammonium persulfate 0.5-1 parts, DNS-86 0.05-0.2 parts, water 250-350 parts.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;4-4.5 times of its weight of ammonium persulfate
Water dissolving;The ammonium persulfate aqueous solution and remaining water for taking 40-50% add reactor, after being warming up to 70-80 DEG C, add 5-
10% pre-emulsion, is to slowly warm up to 82-85 DEG C;After reacting 20-25min, it is water-soluble that remaining pre-emulsion and ammonium persulfate is added dropwise
Liquid, time for adding control in 2-2.5h, 2-2.5h are incubated at a temperature of 85-88 DEG C, is cooled to 55-60 DEG C of discharging;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu amount is to putting into reactor after 50-55%, after being warming up to 85-88 DEG C, premix monomer and ammonium persulfate aqueous solution are added dropwise, during dropwise addition
Between control in 2.5-3h;2-2.5h is incubated after being added dropwise to complete, is cooled to 55-60 DEG C of filtering and discharging;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 7-8 with ammoniacal liquor, the aziridine for adding 0.8% is consolidated
Agent, it is coated on base material;Coating layer water content is baked in 75-115 DEG C of baking oven after the completion of coating to less than 1.5%,
Winding;
(4)Packaging:Finished product after winding is placed in 45-50 DEG C of curing chamber, is cured more than 24h, is cooled to room temperature, is cut
Packaging.
Compared with prior art, it is an advantage of the invention that:The present invention is using distinctive macromole emulsifying agent to natural emulsion
Graft modification is carried out, makes it more preferable with the cohesive force of base material, without carrying out primary coat processing to base material film;Meanwhile with reference to water-based body
The premium properties of system, pollution is few, to more environment-friendly.
Embodiment:
The present invention is described in further detail with reference to embodiments, but these embodiments are not the limit to the present invention
It is fixed.
Embodiment 1
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 10 parts of macromole emulsifying agent, butyl acrylate(BA)18 parts, Isooctyl acrylate monomer(EHA)10
Part, acrylic acid(AA)2 parts, 1 part of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the butyl acrylate of 75 parts by weight(BA)For hydrophobic monomer, the first of 25 parts by weight
Base acrylic acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.1 parts by weight is reaction
Type emulsifying agent, it is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;The water of 4 times of its weight of ammonium persulfate
Dissolving;The ammonium persulfate aqueous solution and remaining water for taking 40% add reactor, after being warming up to 70 DEG C, add 5% pre-emulsion,
It is to slowly warm up to 82 DEG C;After reacting 20min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding is controlled in 2h,
2h is incubated at a temperature of 85 DEG C, is cooled to 55 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 85 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 50% in amount
In 2.5h;2h is incubated after being added dropwise to complete, is cooled to 55 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 7 with ammoniacal liquor, adds 0.8% aziridine solidification
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 75 DEG C of baking oven after the completion of coating, is wound;
(4)Packaging:Finished product after winding is placed in 50 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
Embodiment 2
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 10 parts of macromole emulsifying agent, butyl acrylate(BA)15 parts, Isooctyl acrylate monomer(EHA)13
Part, acrylic acid(AA)2 parts, 1 part of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the butyl acrylate of 75 parts by weight(BA)For hydrophobic monomer, the first of 25 parts by weight
Base acrylic acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.05 parts by weight is anti-
Type emulsifying agent is answered, is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;The water of 4 times of its weight of ammonium persulfate
Dissolving;The ammonium persulfate aqueous solution and remaining water for taking 40% add reactor, after being warming up to 73 DEG C, add 6% pre-emulsion,
It is to slowly warm up to 83 DEG C;After reacting 20min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding is controlled in 2h,
2h is incubated at a temperature of 86 DEG C, is cooled to 55 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 86 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 50% in amount
In 2.5h;2h is incubated after being added dropwise to complete, is cooled to 60 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 7 with ammoniacal liquor, adds 0.8% aziridine solidification
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 85 DEG C of baking oven after the completion of coating, is wound;
(4)Packaging:Finished product after winding is placed in 45 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
Embodiment 3
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 9 parts of macromole emulsifying agent, butyl acrylate(BA)10 parts, Isooctyl acrylate monomer(EHA)13
Part, methyl methacrylate(MMA)5 parts, acrylic acid(AA)2 parts, 1 part of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the butyl acrylate of 75 parts by weight(BA)For hydrophobic monomer, the first of 25 parts by weight
Base acrylic acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.2 parts by weight is reaction
Type emulsifying agent, it is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;4.2 times of its weight of ammonium persulfate
Water dissolves;The ammonium persulfate aqueous solution and remaining water for taking 45% add reactor, after being warming up to 75 DEG C, add 7% pre- breast
Liquid, it is to slowly warm up to 84 DEG C;After reacting 20min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding control exists
2.5h, 2.5h is incubated at a temperature of 88 DEG C, is cooled to 60 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 85 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 55% in amount
In 2.5h;2.5h is incubated after being added dropwise to complete, is cooled to 60 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 7.5 with ammoniacal liquor, the aziridine for adding 0.8% is consolidated
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 90 DEG C of baking oven after the completion of coating, is wound;
(4)Packaging:Finished product after winding is placed in 45 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
Embodiment 4
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 8 parts of macromole emulsifying agent, butyl acrylate(BA)10 parts, Isooctyl acrylate monomer(EHA)13
Part, methyl methacrylate(MMA)5 parts, methacrylic acid(MAA)2 parts, 1 part of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the butyl acrylate of 80 parts by weight(BA)For hydrophobic monomer, the first of 20 parts by weight
Base acrylic acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.1 parts by weight is reaction
Type emulsifying agent, it is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;4.5 times of its weight of ammonium persulfate
Water dissolves;The ammonium persulfate aqueous solution and remaining water for taking 50% add reactor, after being warming up to 80 DEG C, add 9% pre- breast
Liquid, it is to slowly warm up to 85 DEG C;After reacting 22min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding control exists
2h, 2.5h is incubated at a temperature of 88 DEG C, is cooled to 60 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 88 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 55% in amount
In 3h;2.5h is incubated after being added dropwise to complete, is cooled to 55 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 7.5 with ammoniacal liquor, the aziridine for adding 0.8% is consolidated
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 100 DEG C of baking oven after the completion of coating, is received
Volume;
(4)Packaging:Finished product after winding is placed in 50 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
Embodiment 5
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 8 parts of macromole emulsifying agent, butyl acrylate(BA)10 parts, Isooctyl acrylate monomer(EHA)13
Part, methyl methacrylate(MMA)5 parts, methacrylic acid(MAA)2 parts, 3 parts of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the styrene of 80 parts by weight(St)For hydrophobic monomer, the methyl-prop of 20 parts by weight
Olefin(e) acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.1 parts by weight is response type breast
Agent, it is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;The water of 4 times of its weight of ammonium persulfate
Dissolving;The ammonium persulfate aqueous solution and remaining water for taking 50% add reactor, after being warming up to 80 DEG C, add 10% pre- breast
Liquid, it is to slowly warm up to 85 DEG C;After reacting 25min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding control exists
2h, 2h is incubated at a temperature of 88 DEG C, is cooled to 60 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 85 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 50% in amount
In 2.5h;2.5h is incubated after being added dropwise to complete, is cooled to 55 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 8 with ammoniacal liquor, adds 0.8% aziridine solidification
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 110 DEG C of baking oven after the completion of coating, is wound;
(4)Packaging:Finished product after winding is placed in 50 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
Embodiment 6
A kind of environment-friendly type aqueous rubber protective film, is made up of the component comprising following parts by weight:
100 parts of natural emulsion, 6 parts of macromole emulsifying agent, butyl acrylate(BA)8 parts, Isooctyl acrylate monomer(EHA)10
Part, methyl methacrylate(MMA)4 parts, methacrylic acid(MAA)1.5 parts, 1 part of ammonium persulfate.
Wherein:Macromole emulsifying agent is with the styrene of 80 parts by weight(St)For hydrophobic monomer, the methyl-prop of 20 parts by weight
Olefin(e) acid(MAA)For water-soluble monomer, the ammonium persulfate of 0.5 parts by weight is initiator, and the DNS-86 of 0.2 parts by weight is response type breast
Agent, it is prepared by microemulsion polymerization method reaction, water addition is 300 parts by weight.
The preparation method of the environment-friendly type aqueous rubber protective film, comprises the following steps:
(1)The preparation of macromole emulsifying agent:Hydrophobic monomer and water-soluble monomer during macromole emulsifying agent is formulated mix
Close, the water for adding DNS-86 and monomer total amount 50% is standby to monomer progress pre-emulsification;4.5 times of its weight of ammonium persulfate
Water dissolves;The ammonium persulfate aqueous solution and remaining water for taking 40% add reactor, after being warming up to 70 DEG C, add 5% pre- breast
Liquid, it is to slowly warm up to 85 DEG C;After reacting 22min, remaining pre-emulsion and ammonium persulfate aqueous solution is added dropwise, time for adding control exists
2h, 2.3h is incubated at a temperature of 86 DEG C, is cooled to 58 DEG C of dischargings;
(2)The grafting of natural emulsion:The butyl acrylate in film formulation will be protected(BA), Isooctyl acrylate monomer(EHA), first
Base methyl acrylate(MMA), acrylic acid(AA), methacrylic acid(MAA)Five kinds of monomers are pre-mixed;Ammonium persulfate with premix
The water dilution of monomer equivalent;By natural emulsion and step(1)Obtained macromole emulsifying agent is mixed by formula ratio, adds water adjustment to contain
Gu after being warming up to 86 DEG C, premix monomer and ammonium persulfate aqueous solution, time for adding control is added dropwise to reactor is put into after 50% in amount
In 2.8h;2h is incubated after being added dropwise to complete, is cooled to 58 DEG C of filtering and dischargings;
(3)Coating:The pH value of the natural emulsion after grafting is adjusted to 8 with ammoniacal liquor, adds 0.8% aziridine solidification
Agent, it is coated on base material;Coating layer water content is baked to less than 1.5% in 115 DEG C of baking oven after the completion of coating, is wound;
(4)Packaging:Finished product after winding is placed in 50 DEG C of curing chamber, cures more than 24h, is cooled to room temperature, cutting bag
Dress.
The aqueous rubber diaphragm that various embodiments above is prepared, grafting stability, peel strength, degumming situation and
The test result of viscous force change is as shown in the table: