CN107828025A - A kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values and preparation method thereof - Google Patents
A kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values and preparation method thereof Download PDFInfo
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- CN107828025A CN107828025A CN201711084585.XA CN201711084585A CN107828025A CN 107828025 A CN107828025 A CN 107828025A CN 201711084585 A CN201711084585 A CN 201711084585A CN 107828025 A CN107828025 A CN 107828025A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values and preparation method thereof, the emulsion includes water-and acrylate emulsion host and curing agent, and the mass ratio of the water-and acrylate emulsion host and curing agent is 100：(3 6), wherein, water-and acrylate emulsion host includes the raw material of following parts by weight：50 80 parts of deionized water, 0.6 1.4 parts of emulsifying agent, 19 49 parts of mix monomer, 0.3 0.5 parts of initiator；This method comprises the following steps：A, pre-emulsion is prepared；B, seed emulsion is prepared；C, water-and acrylate emulsion is prepared；D, property acrylic acid ester emulsion host and the curing agent containing polyisocyanates are used cooperatively.Beneficial effects of the present invention：The peel strength of composite membrane is greatly improved, and changes the compound rear tacky phenomenon of glued membrane of traditional aqueous binder and is applicable the less disadvantage of structure of composite membrane.
Description
Technical field
The invention belongs to adhesive field, and in particular to a kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values
And preparation method thereof.
Background technology
With the continuous enhancing of people's environmental consciousness, environmentally friendly laws and regulations are also in continuous appearance and perfect, all row
The direction that industry is made joint efforts all is environmental protection, green, health.Composite membrane industry development reduces and removed compound middle use to today
Organic solvent become a kind of inevitable trend, environment amenable aqueous laminating adhesive can progressively substitute solvent-type film-covered
Glue, still, currently it can not also substitute organic solvent type adhesive completely in composite membrane field, a big chunk reason is traditional
Performance of the water-base cement in many composite constructions is unable to reach or the level close to organic solvent type adhesive.
Traditional aqueous laminating adhesive has the problems such as peel strength is low, and glue-line is tacky, structure of composite membrane is simple, single to limit because of it
The development of aqueous laminating adhesive is made.For example, traditional water-and acrylate emulsion, when carrying out Tg temperature designs, in order to ensure
Composite membrane has certain peel strength, often the very low of Tg temperature designs, although so design can ensure aqueous laminating adhesive
With certain peel strength, but many negative effects are therefore also brought, for example glue-line is once tacky, in later stage composite membrane system
During bag, it may occur that the problem of peel strength deep fades, these problems limit water-base cement in many composite constructions
Performance is unable to reach or the level close to organic solvent type adhesive.
The content of the invention
The technical problem to be solved in the present invention is how to provide a kind of double-component aqueous acrylate of composite membrane high tg values
Emulsion and preparation method thereof, in the preparation process of emulsion, by designing the Tg values of acrylate copolymer, make glue-line dry and comfortable,
Peel strength can be greatly improved by introducing curing agent, widen the application field of aqueous laminating adhesive, so as to solve above-mentioned skill
Art problem.
A kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values of the present invention, including water-and acrylate emulsion master
The mass ratio of agent and curing agent, the water-and acrylate emulsion host and curing agent is 100：(3-6), wherein, aqueous acrylamide
Acid esters emulsion host includes the raw material of following parts by weight：The deionized water of 50-80 parts, the emulsifying agent of 0.6-1.4 parts, 19-49
The mix monomer, the initiator of 0.3-0.5 parts of part.
Preferably, the emulsifying agent is the emulsifying agent without APEO.
Preferably, the emulsifying agent without APEO is alkyl alcohol ethoxylates ammonium sulfate, alkyl alcohol ethoxylates
Sodium sulphate, allyloxy alkyl alcohol ethoxylates ammonium sulfate, nonyl alcohol APEO, allyloxy alkylol polyoxyethylene
At least one in ether, alkyl alcohol ethoxylates sodium sulfonate, the sodium sulphate of alkyl diphenyl base ether two, alkyl diphenyl base ether sodium disulfonate
Kind.
Further, the mix monomer includes the raw material of following percentage by weight：Ethyl acrylate 3-30%, acrylic acid
Butyl ester 16.5-70%, Isooctyl acrylate monomer 2-10%, methyl methacrylate 13-40%, acrylic acid 0.4-1.5%, acrylic acid
Hydroxyl ethyl ester 0.5-2%, mix monomer Tg temperature ranges are -15 DEG C to -5 DEG C.
Preferably, the initiator is at least one of ammonium persulfate, potassium peroxydisulfate.
Preferably, the curing agent is the curing agent containing polyisocyanates, and the curing agent containing polyisocyanates is 1,
6- hexylidene diisocyanates, IPDI, trimethyl 1,6- hexylidene diisocyanates, hexa-methylene two are different
At least one of cyanate, trans cyclohexane diisocyanate.
Present invention also offers a kind of preparation method of the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values, specifically
Comprise the following steps：
A, pre-emulsion is prepared：By the deionized water of 35-50 parts, the emulsifying agent of 0.5-0.9 parts, 15-34 parts mixing list
Body and the initiator of 0.2-0.3 parts are added to progress pre-emulsification 25-30 minutes in emulsifying kettle, obtain pre-emulsion；
B, seed emulsion is prepared：By the deionized water of 15-30 parts, the emulsifying agent of 0.1-0.5 parts, 4-15 parts mix monomer
Put into the initiator of 0.1-0.2 parts in reactor, be warming up to 70-80 DEG C, carry out emulsion polymerization, 10-30 points of reaction
Seed emulsion is made in clock；
C, water-and acrylate emulsion host is prepared：The pre-emulsion prepared in step A is added dropwise to described in step B
In seed emulsion, time for adding is 2-6 hours, and reaction temperature control is incubated 1-2 hours after 70-90 DEG C, completion of dropwise addition, then
It is cooled to 40-50 DEG C, adds ammoniacal liquor or sodium hydroxide adjusts PH between 6-8, obtaining water-and acrylate emulsion host；
D, double-component aqueous acrylic acid ester emulsion is prepared：By the water-and acrylate emulsion host prepared in step C with
Curing agent compatibility containing polyisocyanates, wherein, the mass ratio of the water-and acrylate emulsion host and curing agent is 100：
(3-6), obtain double-component aqueous acrylic acid ester emulsion.
Further, in step B, temperature is raised to 75-80 DEG C during emulsion polymerization, and reaction obtains seed emulsion in 20 minutes.
Further, in step C, described pre-emulsification agent is added dropwise for 4 hours, and the reaction temperature control is in 80-90
DEG C, after being incubated 1 hour, it is cooled to 50 DEG C.
Further, in step D, the curing agent containing polyisocyanates will pour into water-and acrylate emulsion host
In stir, after the curing agent containing polyisocyanates pours into, continue stirring more than 10 minutes, can use.
Compared with prior art, the present invention has the advantages that：Substantially increase the performance of aqueous binder so that
Aqueous binder is able to be applied in wider structure of composite membrane, for example, Polar Crystal Slab PET//PE, PET//CPP and
The structures such as sandwich diaphragm structure BOPP//VMPET//PE, BOPP//VMPET//CPP, it is dry and comfortable in glue-line, in terms of peel strength
The level of solvent type adhesive is reached, has thus further widened the application of aqueous binder, so as to accelerate water
Property adhesive substitution organic solvent type adhesive paces, solvent borne polyurethane glue can be substituted extensively, greatly reduced organic molten
The discharge capacity of agent, safety and environmental protection is pollution-free, is had a wide range of applications in composite membrane field, can be made for environmental protection cause
Due contribution.
Embodiment
With reference to embodiment, the embodiment of the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
The present invention adjusts the Tg of acrylate copolymer during composite membrane water-and acrylate emulsion is prepared
Height, make glue-line dry and comfortable, water-and acrylate emulsion is made, then the emulsion and curing agent are arranged in pairs or groups, so as to obtain the double groups of high tg values
Part water-and acrylate emulsion, and have more preferable peel strength than traditional composite membrane water-and acrylate emulsion, more
Good application.
A kind of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values of the present invention, including water-and acrylate emulsion master
The mass ratio of agent and curing agent, the water-and acrylate emulsion host and curing agent is 100：(3-6), wherein, aqueous acrylamide
Acid esters emulsion host includes the raw material of following percentage by weight：The deionized water of 50-80 parts, the emulsifying agent of 0.6-1.4 parts, 19-
49 parts of mix monomer, the initiator of 0.3-0.5 parts.
The emulsifying agent is the emulsifying agent without APEO, and the emulsifying agent without APEO is alkyl alcohol ethoxylates sulphur
Sour ammonium, alkyl alcohol ethoxylates sodium sulphate, allyloxy alkyl alcohol ethoxylates ammonium sulfate, nonyl alcohol APEO,
Allyloxy alkyl alcohol ethoxylates, alkyl alcohol ethoxylates sodium sulfonate, the sodium sulphate of alkyl diphenyl base ether two, alkyl diphenyl
At least one of base ether sodium disulfonate.
The mix monomer includes the raw material of following percentage by weight：Ethyl acrylate 3-30%, butyl acrylate 16.5-
70%th, Isooctyl acrylate monomer 2-10%, methyl methacrylate 13-40%, acrylic acid 0.4-1.5%, hydroxy-ethyl acrylate
0.5-2%, mix monomer Tg temperature ranges are -15 DEG C to -5 DEG C.
The initiator is at least one of ammonium persulfate, potassium peroxydisulfate.
The curing agent is the curing agent containing polyisocyanates, and the curing agent containing polyisocyanates is 1,6- hexylidenes
Diisocyanate (HDI), IPDI (IPDI), trimethyl 1,6- hexylidene diisocyanates (TMHDI), six
At least one of methylene diisocyanate (HMDI), trans cyclohexane diisocyanate (CHDI).
Present invention also offers a kind of preparation method of the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values, specifically
Comprise the following steps：
A, pre-emulsion is prepared：At room temperature, by the deionized water of 35-50 parts, the emulsifying agent of 0.5-0.9 parts, 15-34 parts
Mix monomer and the initiator of 0.2-0.3 parts be added in emulsifying kettle progress pre-emulsification 25-30 minutes, obtain pre-emulsion；
B, seed emulsion is prepared：By the deionized water of 15-30 parts, the emulsifying agent of 0.1-0.5 parts, 4-15 parts mix monomer
Put into the initiator of 0.1-0.2 parts in reactor, be warming up to 70-80 DEG C, carry out emulsion polymerization, 10-30 points of reaction
Seed emulsion is made in clock；
Here, in the above-mentioned preparation method of the present invention, pre-emulsion and seed emulsion prepared by step A and step B, two
For person because the quality of the emulsifying agent of addition, mix monomer, initiator, deionized water is different, the container of reaction is different, the reaction time
Difference, so the emulsion prepared is distinct.
In step A and step B, the emulsifying agent is the emulsifying agent without APEO, because APEO is to environment, there is danger
Evil, environmental-protection function can be played using the emulsifying agent without APEO.
C, water-and acrylate emulsion host is prepared：The pre-emulsion prepared in step A is added dropwise to described in step B
In seed emulsion, time for adding is 2-6 hours, and reaction temperature control is incubated 1-2 hours after 70-90 DEG C, completion of dropwise addition, then
It is cooled to 40-50 DEG C, adds ammoniacal liquor or sodium hydroxide adjusts PH between 6-8, obtaining water-and acrylate emulsion host；
D, double-component aqueous acrylic acid ester emulsion is prepared：By the water-and acrylate emulsion host prepared in step C with
Curing agent compatibility containing polyisocyanates, wherein, the mass ratio of the water-and acrylate emulsion host and curing agent is 100：
(3-6), double-component aqueous acrylic acid ester emulsion is obtained, the emulsion need to use within 8 hours.
In step B, temperature is raised to 75-80 DEG C during emulsion polymerization, and reaction obtains seed emulsion in 20 minutes.
In step C, described pre-emulsification agent is added dropwise for 4 hours, and at 80-90 DEG C, insulation 1 is small for the reaction temperature control
Shi Hou, it is cooled to 50 DEG C.
In step D, the curing agent containing polyisocyanates will be poured into water-and acrylate emulsion host and stirred
It is even, after the curing agent containing polyisocyanates pours into, continue stirring more than 10 minutes, can use.
Present disclosure is described in further detail with reference to embodiment 1-6 and testing result.
Embodiment 1
35 grams of deionized water, 0.5 gram of emulsifying agent, 0.2 gram of initiation and 15 grams of mix monomer are first put into breast
Change in kettle and carry out pre-emulsification, obtain pre-emulsion, then by remaining 15 grams of deionized waters, 0.1 gram of emulsifying agent, 0.1 gram of initiation
Agent, 4 grams of mix monomers put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, react 20 minutes, obtain seed breast
Liquid, wherein, Tg values are -12 DEG C, and then the pre-emulsion of whole is added dropwise in seed emulsion again, and time for adding is 4 hours,
Reaction temperature is 80-85 DEG C, after being added dropwise, is incubated 1 hour, and then holding temperature is cooled to 50 DEG C at 80-85 DEG C, use
25% ammoniacal liquor adjusts pH value between 6-8, obtaining the water-and acrylate emulsion host；
Curing agent trimethyl 1,6- hexylidene diisocyanates (TMHDI) are taken slowly to pour into water-and acrylate emulsion master
Stirred in agent, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate
The mass ratio of emulsion/1,6- hexylidene diisocyanates (HDI) is 100：4.
Embodiment 2
50 grams of deionized water, 0.9 gram of emulsifying agent, 0.3 gram of initiation and 34 grams of mix monomer are first put into breast
Change in kettle and carry out pre-emulsification, obtain pre-emulsion, then by remaining 30 grams of deionized waters, 0.5 gram of emulsifying agent, 0.2 gram of initiation
Agent, 15 grams of mix monomers put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, react 20 minutes, obtain seed breast
Liquid, wherein, Tg values are -12 DEG C, and then the pre-emulsion of whole is added dropwise in seed emulsion again, and time for adding is 4 hours,
Reaction temperature is 80-85 DEG C, after being added dropwise, is incubated 1 hour, and then holding temperature is cooled to 50 DEG C at 80-85 DEG C, use
25% ammoniacal liquor adjusts pH value between 6-8, obtaining the water-and acrylate emulsion host；
Take curing agent 1,6- hexylidene diisocyanates (HDI) slowly to pour into water-and acrylate emulsion host to stir
Uniformly, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate emulsion/1,6-
The mass ratio of hexylidene diisocyanate (HDI) is 100：4.
Table 1 is the composition and dosage of material needed for embodiment 3-6
Embodiment 3
First 40.81 grams of deionized water, 0.6 gram of emulsifying agent, 0.3 gram of initiation and 28.14 grams of mix monomer are thrown
Enter into emulsifying kettle and carry out pre-emulsification, obtain pre-emulsion, then by remaining 17.49 grams of deionized waters, 0.4 gram of emulsifying agent,
0.2 gram of initiator, 12.06 grams of mix monomers put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, react 20 points
Clock, seed emulsion is obtained, wherein, Tg values are -12 DEG C, and then the pre-emulsion of whole is added dropwise in seed emulsion again, are dripped
It is 4 hours between added-time, reaction temperature is 80-85 DEG C, after being added dropwise, is incubated 1 hour, then holding temperature drops at 80-85 DEG C
Temperature adjusts pH value between 6-8, obtaining the water-and acrylate emulsion host to 50 DEG C, with 25% ammoniacal liquor；
Take curing agent 1,6- hexylidene diisocyanates (HDI) slowly to pour into water-and acrylate emulsion host to stir
Uniformly, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate emulsion/1,6-
The mass ratio of hexylidene diisocyanate (HDI) is 100：4.
Method of testing：
Using dry type composite algorithm, on dry compound machine compound NY//CPP, NY//PE, PET//CPP, PET//PE,
The isostructural composite membrane of BOPP//VMPET//CPP, BOPP//VMPET//PE, is tested according to GB/T8808-1988 standards,
Test result is shown in Table 2.
Table 2 is the test result list figure of experiment test in embodiment 3 in the present invention
Embodiment 4
First by 38.025 grams of deionized water, 0.8 gram of emulsifying agent, 0.25 gram of initiator and 32 grams of monomer mixed solution
Put into and pre-emulsification is carried out in emulsifying kettle, and obtain pre-emulsion, then by remaining 20.475 parts of deionized waters, 0.2 part of breast
Agent, 0.25 part of initiator, 8 parts of mix monomers put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, react 20 points
Clock, seed emulsion is obtained, wherein, Tg values are -10 DEG C, and then the pre-emulsion of whole is added dropwise in seed emulsion again, are added dropwise
Time is 4 hours, and reaction temperature is 80-85 DEG C, after being added dropwise, is incubated 1 hour, holding temperature is 80-85 DEG C, is then dropped
Temperature adjusts pH value between 6-8, obtaining the water-and acrylate emulsion to 50 DEG C, with 25% ammoniacal liquor.
Take curing agent 1,6- hexylidene diisocyanates (HDI) slowly to pour into water-and acrylate emulsion host to stir
Uniformly, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate emulsion/1,6-
The mass ratio of hexylidene diisocyanate (HDI) is 100：5.
Method of testing：
Using dry type composite algorithm, on dry compound machine compound NY//CPP, NY//PE, PET//CPP, PET//PE,
The isostructural composite membrane of BOPP//VMPET//CPP, BOPP//VMPET//PE, is tested according to GB/T8808-1988 standards,
Test result is shown in Table 3.
Table 3 is the test result list figure of experiment test in embodiment 4 in the present invention
Embodiment 5
First by 43.875 grams of deionized water, 0.8 gram of emulsifying agent, 0.25 gram of initiator and 28 grams of monomer mixed solution
Put into and pre-emulsification is carried out in emulsifying kettle, and obtain pre-emulsion, then by remaining 14.625 grams of deionized waters, 0.2 gram of breast
Agent, 0.25 gram of initiator, 12 grams of mix monomers are put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, reaction
20 minutes, seed emulsion is obtained, wherein, Tg values are -8 DEG C, and then the pre-emulsion of whole is added drop-wise in seed emulsion again, are dripped
It is 4 hours between added-time, reaction temperature is 80-85 DEG C, after being added dropwise, is incubated 1 hour, holding temperature is 80-85 DEG C, is then dropped
Temperature adjusts pH value between 6-8, obtaining the water-and acrylate emulsion to 50 DEG C, with 25% ammoniacal liquor.
Take curing agent IPDI (IPDI) slowly to pour into water-and acrylate emulsion host to stir
Uniformly, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate emulsion/different Buddhist
The mass ratio of your ketone diisocyanate (IPDI) is 100：5.
Method of testing：
Using dry type composite algorithm, on dry compound machine compound NY//CPP, NY//PE, PET//CPP, PET//PE,
The isostructural composite membrane of BOPP//VMPET//CPP, BOPP//VMPET//PE, is tested according to GB/T8808-1988 standards,
Test result is shown in Table 4.
Table 4 is the test result list figure of experiment test in embodiment 5 in the present invention；
Embodiment 6
First 43.875 grams of deionized water, 0.8 gram of emulsifying agent, 0.3 gram of initiator and 28 grams of mix monomer are thrown
Enter into emulsifying kettle and carry out pre-emulsification, and obtain pre-emulsion, then by remaining 14.625 grams of deionized waters, 0.2 gram of emulsification
Agent, 0.2 gram of initiator and 12 grams of mix monomers put into reactor, are warming up to 75-80 DEG C, carry out polymerisation, reaction 20
Minute, seed emulsion is obtained, wherein, Tg values are -5 DEG C, and then the pre-emulsion of whole is added dropwise in seed emulsion again, are added dropwise
4 hours time, 80-85 DEG C of reaction temperature, after being added dropwise, 1 hour is incubated, 80-85 DEG C of holding temperature, is then cooled to 50
DEG C, pH value is adjusted between 6-8, obtaining the water-and acrylate emulsion with 25% ammoniacal liquor.
Take curing agent hexamethylene diisocyanate (HMDI) slowly to pour into water-and acrylate emulsion host to stir
Uniformly, after curing agent pours into, continue stirring more than 10 minutes, can use, wherein, water-and acrylate emulsion/six are sub-
The mass ratio of methyl diisocyanate (HMDI) is 100：6.
Method of testing：
Using dry type composite algorithm, on dry compound machine compound NY//CPP, NY//PE, PET//CPP, PET//PE,
The isostructural composite membrane of BOPP//VMPET//CPP, BOPP//VMPET//PE, is tested according to GB/T8808-1988 standards,
Test result is shown in Table 5.
Table 5 is the test result list figure of experiment test in embodiment 6 in the present invention.
The present invention designs different Tg temperature by adjusting the ratio of reaction monomers when preparing water-and acrylate emulsion
Degree, the double-component aqueous acrylic acid ester emulsion obtained by the curing agent species and dosage of arranging in pairs or groups different all have good stripping
Intensity.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.
Claims (10)
1. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 1, it is characterised in that：Including
The mass ratio of water-and acrylate emulsion host and curing agent, the water-and acrylate emulsion host and curing agent is 100：
(3-6), wherein, water-and acrylate emulsion host includes the raw material of following parts by weight：The deionized water of 50-80 parts, 0.6-
1.4 parts of emulsifying agent, the mix monomer of 19-49 parts, the initiator of 0.3-0.5 parts.
2. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 1, it is characterised in that：It is described
Emulsifying agent is the emulsifying agent without APEO.
3. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 2, it is characterised in that：It is described
Emulsifying agent without APEO is alkyl alcohol ethoxylates ammonium sulfate, alkyl alcohol ethoxylates sodium sulphate, allyloxy alkyl
Alcohol polyoxyethylene ether ammonium sulfate, nonyl alcohol APEO, allyloxy alkyl alcohol ethoxylates, alkyl alcohol ethoxylates
At least one of sodium sulfonate, the sodium sulphate of alkyl diphenyl base ether two, alkyl diphenyl base ether sodium disulfonate.
4. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 1, it is characterised in that：It is described
Mix monomer includes the raw material of following percentage by weight：Ethyl acrylate 3-30%, butyl acrylate 16.5-70%, acrylic acid
Different monooctyl ester 2-10%, methyl methacrylate 13-40%, acrylic acid 0.4-1.5%, hydroxy-ethyl acrylate 0.5-2%, mixing are single
Body Tg temperature ranges are -15 DEG C to -5 DEG C.
5. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 1, it is characterised in that：It is described
Initiator is at least one of ammonium persulfate, potassium peroxydisulfate.
6. the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 1, it is characterised in that：It is described
Curing agent is the curing agent containing polyisocyanates, the curing agent containing polyisocyanates be 1,6- hexylidene diisocyanates,
IPDI, trimethyl 1,6- hexylidene diisocyanates, hexamethylene diisocyanate, trans cyclohexane two
At least one of isocyanates.
A kind of 7. system of double-component aqueous acrylic acid ester emulsion of composite membrane high tg values using described in claim any one of 1-6
Preparation Method, it is characterised in that：Comprise the following steps：
A, pre-emulsion is prepared：By the deionized water of 35-50 parts, the emulsifying agent of 0.5-0.9 parts, 15-34 parts mix monomer and
The initiator of 0.2-0.3 parts is added to progress pre-emulsification 25-30 minutes in emulsifying kettle, obtains pre-emulsion；
B, seed emulsion is prepared：By the deionized water of 15-30 parts, the emulsifying agent of 0.1-0.5 parts, 4-15 parts mix monomer and
The initiator of 0.1-0.2 parts is put into reactor, is warming up to 70-80 DEG C, carries out emulsion polymerization, reacts 10-30 minutes
Seed emulsion is made；
C, water-and acrylate emulsion host is prepared：The pre-emulsion prepared in step A is added dropwise to the seed described in step B
In emulsion, time for adding is 2-6 hours, and reaction temperature control is incubated 1-2 hours after 70-90 DEG C, completion of dropwise addition, then cooled
To 40-50 DEG C, add ammoniacal liquor or sodium hydroxide and adjust PH between 6-8, obtaining water-and acrylate emulsion host；
D, double-component aqueous acrylic acid ester emulsion is prepared：The water-and acrylate emulsion host prepared in step C is more with containing
The curing agent compatibility of isocyanates, wherein, the mass ratio of the water-and acrylate emulsion host and curing agent is 100：(3-
6) double-component aqueous acrylic acid ester emulsion, is obtained.
8. the preparation method of the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 7, it is special
Sign is：In step B, temperature is raised to 75-80 DEG C during emulsion polymerization, and reaction obtains seed emulsion in 20 minutes.
9. the preparation method of the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 7, it is special
Sign is：In step C, described pre-emulsification agent is added dropwise for 4 hours, and at 80-90 DEG C, insulation 1 is small for the reaction temperature control
Shi Hou, it is cooled to 50 DEG C.
10. the preparation method of the double-component aqueous acrylic acid ester emulsion of composite membrane high tg values according to claim 7, it is special
Sign is：In step D, the curing agent containing polyisocyanates will be poured into water-and acrylate emulsion host and stirred
It is even, after the curing agent containing polyisocyanates pours into, continue stirring more than 10 minutes, can use.
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