CN115215968B - Preparation method of hybrid acrylic resin glue - Google Patents
Preparation method of hybrid acrylic resin glue Download PDFInfo
- Publication number
- CN115215968B CN115215968B CN202210858086.6A CN202210858086A CN115215968B CN 115215968 B CN115215968 B CN 115215968B CN 202210858086 A CN202210858086 A CN 202210858086A CN 115215968 B CN115215968 B CN 115215968B
- Authority
- CN
- China
- Prior art keywords
- styrene
- acrylate
- butadiene emulsion
- acrylic
- acrylic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003292 glue Substances 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000002174 Styrene-butadiene Substances 0.000 claims abstract description 37
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000839 emulsion Substances 0.000 claims abstract description 37
- 239000011115 styrene butadiene Substances 0.000 claims abstract description 37
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 acrylic ester Chemical class 0.000 claims abstract description 11
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims abstract description 9
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 238000009396 hybridization Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical group CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C09J151/04—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 rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application discloses a preparation method of hybrid acrylic resin glue, which comprises deionized water, styrene-butadiene emulsion, an acrylic ester monomer, a surfactant and an initiator in a preparation reaction system, wherein the acrylic ester monomer comprises butyl acrylate, isooctyl acrylate, methyl methacrylate, hydroxyethyl acrylate, acrylic acid and the like, and the initiator is sodium persulfate, sodium bisulfite, tert-butyl hydroperoxide or the like. The glue prepared by the method has the following beneficial effects: by grafting acrylic resin on the styrene-butadiene emulsion, the hybridization modification of the acrylic resin is realized, the adhesion force of the aqueous acrylic pressure-sensitive adhesive can be obviously improved, and the stripping force of the aqueous acrylic pressure-sensitive adhesive is not reduced.
Description
Technical Field
The invention relates to the field of glue preparation, in particular to a preparation method of hybrid acrylic resin glue.
Background
The aqueous pressure-sensitive adhesive is widely applied to the fields of labels, advertisement materials, back coating of aqueous composite materials and the like, and the traditional aqueous pressure-sensitive adhesive is mainly an aqueous acrylic resin system. A disadvantage of aqueous acrylic resins is that the water-borne acrylic resins have relatively poor holding power (i.e., cohesive force), and in order to improve the holding power of the aqueous acrylic resins, it is common to add a hinge monomer to the aqueous acrylic resin system, but adding a hinge monomer can increase the holding power of the entire system (i.e., improve cohesive force), but this reduces the peel force of the entire aqueous pressure-sensitive adhesive.
Disclosure of Invention
The invention provides a preparation method of hybrid acrylic resin glue aiming at the problems.
The technical scheme adopted by the invention is as follows:
The preparation method of the hybrid acrylic resin glue comprises the steps of preparing a reaction system from deionized water, styrene-butadiene emulsion, an acrylic ester monomer, a surfactant and an initiator, wherein the acrylic ester monomer comprises butyl acrylate, isooctyl acrylate, methyl methacrylate, hydroxyethyl acrylate, acrylic acid and the like, and the initiator is sodium persulfate, sodium bisulfite, tert-butyl hydroperoxide or the like.
The styrene-butadiene emulsion can be styrene-butadiene emulsion with tg (glass transition temperature) between-40 ℃ and 0 ℃, and the Ding Benru dissolution rate in the invention is more than or equal to 80 percent. The dissolution rate is a measure of the hinge density, and is typically obtained by drying a styrene-butadiene emulsion to form a film, then taking a certain amount of dry film to soak in toluene for 24 hours, then filtering and weighing, and dividing the difference in mass between the front and rear by the middle of the resin before soaking. The styrene-butadiene emulsion is used as a part of a hybrid resin, can be used as a seed for emulsion polymerization, and can also be used as a microreactor for emulsion polymerization.
The acrylate monomers (i.e., butyl acrylate, isooctyl acrylate, methyl methacrylate, and hydroxyethyl acrylate) are the polymer monomers that make up the acrylic resin, and are the main monomer combinations that make up the acrylic resin portion of the hybrid system, and undergo free radical polymerization during the polymerization process to form the acrylic resin polymer.
The surfactant is an emulsifying monomer and plays a role of stabilizing emulsion particles, and the commonly used surfactant is sodium alkyl sulfate, sodium alkyl sulfonate, sodium alkoxy sulfonate, or sodium alkoxy sulfate, sodium succinate sulfonate, etc., such as sodium dodecyl benzene sulfonate.
Sodium persulfate, sodium bisulphite and tert-butyl hydroperoxide are free radical polymerization initiators, and decompose under the condition of addition to generate free radicals, and then the acrylic acid monomers are polymerized through the free radicals.
The styrene-butadiene emulsion is obtained by polymerizing butadiene and styrene, the polybutadiene is elastic rubber, and the hardness can be regulated after the styrene is added. Thus, the polymer of styrene-butadiene has good elasticity, which is incomparable with acrylic resins. Since during polymerization butadiene has two double bonds, typically one active double bond, this double bond is capable of undergoing a hinge reaction to build up a network. Thus, the styrene-butadiene emulsion generally has higher hinge density. The degree of articulation can generally be characterized by the rate of dissolution, the lower the rate of dissolution, the higher the degree of articulation, and instead the lower the degree of articulation. The double bonds which are not polymerized usually can remain a part to the end and can not fully react in the process of polymerization of the styrene-butadiene emulsion, and the double bonds can be oxidized in the later use process, so that the ageing property of the styrene-butadiene emulsion is not very good, and the performances such as elasticity, viscosity and the like are easily lost.
The following diagram shows the polymer chain structure of a general styrene-butadiene emulsion (i.e., a butadiene-styrene copolymer).
The invention introduces acrylic resin into the system by copolymerization based on the original styrene-butadiene emulsion. Acrylic resin is a pressure-sensitive adhesive material widely used, the tg is generally between-40 ℃ and-60 ℃, the acrylic resin is obtained by copolymerizing acrylic ester monomers, butyl acrylate and isooctyl acrylate are commonly used monomers with low tg (namely monomers with tg of homopolymers lower than-20 ℃), so that the content of the acrylic resin in the general pressure-sensitive adhesive is generally between 70% and 90%, other hard monomers (namely monomers with tg of homopolymers higher than 0 ℃) such as methyl methacrylate and styrene play a role in adjusting tg and also play a role in improving cohesion, and hinge monomers such as 1, 4-butanediol diacrylate are added, the tg of the corresponding polymer is 45 ℃, the cohesion is improved by playing a role of a hinge, and the general addition amount is between 0.01% and 2%. However, the above method reduces the peeling force while improving the cohesive force. The cohesive force and the peeling force are a pair of teeterboards, the cohesive force is improved by improving tg (increasing the proportion of hard monomers), the peeling force is reduced by improving tg, and the common pressure-sensitive adhesive has the advantages that tg of the hard monomer methyl methacrylate or styrene is between minus 60 ℃ and minus 40 ℃, and the other hard monomer methyl methacrylate or styrene has the advantages of increasing the hinge monomer such as 1, 4-butanediol diacrylate, and the effect is not obvious when the adding amount is small such as 0.01%, the effect is not obvious, the hinge density is not big, the viscosity (peeling force is reduced) is reduced after the adding amount is large such as 0.1%, the hinge density is too big, one reason is that tg of the self-polymer is at 45 ℃, the second reason is that the double bonds at two end positions are relatively active, and the hinge with other acrylate monomers is sufficient, and therefore, the cohesive force and the peeling force are difficult to balance in a system made of acrylic resin.
The general structure of the acrylic pressure-sensitive adhesive is as follows.
Based on the above reasons, the scheme utilizes the unit that the residual double bond in the structure can further provide a hinge in the styrene-butadiene emulsion, and the tg of the styrene-butadiene emulsion is between-40 ℃ and 0 ℃ and can better balance the hinge density in the system without losing tg. Therefore, the hybridization process provided by the invention has obvious advantages of balancing cohesive force and peeling force, and the peeling force is not reduced while the cohesive force is increased. Meanwhile, in the polymerization process, double bonds remained in the styrene-butadiene emulsion can be reacted in a further step, so that the ageing resistance of the system can be obviously improved. By combining the principle, the cohesive force and the stripping force can be effectively balanced, the stripping force is not reduced while the cohesive force is improved, and meanwhile, the good ageing resistance of the acrylic resin system can be maintained.
According to the preparation method, the acrylic resin is grafted on the styrene-butadiene emulsion, so that the hybridization modification of the acrylic resin is realized, the adhesion force of the aqueous acrylic pressure-sensitive adhesive can be remarkably improved, and the stripping force of the aqueous acrylic pressure-sensitive adhesive is not reduced.
Optionally, the Tg of the styrene-butadiene emulsion is-40-0 ℃, and the dissolution rate is more than 80%.
Optionally, the solid content of the styrene-butadiene emulsion is 45% -55%.
Optionally, the reaction is completed to adjust the pH of the mixture to between 8 and 9.
Optionally, the styrene-butadiene emulsion is added into deionized water, and then acrylate monomers including butyl acrylate, isooctyl acrylate, methyl methacrylate, hydroxyethyl acrylate, acrylic acid and the like are added
Alternatively, butyl acrylate or isooctyl acrylate (both are soft acrylate monomers), and their mass or mass ratio is 70% -90% of the total acrylate monomer component.
Optionally, the mass ratio of the styrene-butadiene emulsion to the acrylic ester monomer is 0.3:1 to 0.5:1.
Optionally, the surfactant is sodium alkyl sulfate or sodium alkyl sulfonate or sodium alkoxy sulfate or sodium succinic sulfonate, and the like, and also can be sodium dodecyl benzene sulfonate.
The beneficial effects of the invention are as follows: by grafting acrylic resin on the styrene-butadiene emulsion, the hybridization modification of the acrylic resin is realized, the adhesion force of the aqueous acrylic pressure-sensitive adhesive can be obviously improved, and the stripping force of the aqueous acrylic pressure-sensitive adhesive is not reduced.
The specific embodiment is as follows:
The present invention will be described in detail with reference to the following examples.
Example 1
150 G of water and 50g of styrene-butadiene emulsion with solid content of 50% are placed at the bottom of a reaction kettle, tg of the styrene-butadiene emulsion is-40 ℃, and dissolution rate is more than 80%, then the temperature is raised to 85 ℃,11 g of 10% sodium persulfate solution is started to be added dropwise, after 5 minutes, a mixture of monomers, namely 140 g of butyl acrylate, 10g of methyl methacrylate, 2g of hydroxyethyl acrylate, 2g of acrylic acid, 3g of 25% surfactant sodium dodecyl benzene sulfonate solution and 52g of deionized water, is started to be added dropwise. The dropping time is 60 minutes, and the temperature in the reaction kettle is controlled at 85 ℃ during the dropping. After the monomer was added dropwise, the temperature in the reaction vessel was maintained at 85 ℃. And held for 30 minutes. Then 1g of 70% tertiary butyl hydrogen peroxide solution is added, then 12 g of 7% sodium bisulphite aqueous solution is added dropwise, the temperature in the reaction kettle is controlled to be more than 65 ℃ in the dropwise adding process, and the dropwise adding time is 60 minutes. Then ammonia water is added to adjust the pH value to 8-9 after the temperature of the whole reaction system is cooled to below 25 ℃.
Example 2
100 G of deionized water is added at the bottom of a reaction kettle, 3g of sodium dodecyl benzene sulfonate solution with the concentration of 25% is added after the reaction kettle is filled for a year, then 2g of styrene-butadiene emulsion with the solid content of 50% is added, the Tg of the styrene-butadiene emulsion is-40 ℃, the dissolution rate is more than 80%, monomers which are 70 g of butyl acrylate, 5g of methyl methacrylate, 1g of hydroxyethyl acrylate and 1g of acrylic acid are gradually added while stirring. After stirring for 30 minutes. The temperature is maintained at room temperature, typically between 25℃and 30 ℃. After the subsequent addition of nitrogen for 30 minutes, the addition of 0.4 g of a 70% solution of tert-butyl hydrogen peroxide and 6g of sodium hydrogen sulfite at a concentration of 10% was started in one portion. The temperature was initially raised gradually to between 60 and 70 c with stirring, and then a mixture of monomers, 70 g butyl acrylate, 5g methyl methacrylate, 1g hydroxyethyl acrylate, 1g acrylic acid, 1g sodium dodecyl benzene sulfonate as a 25% strength surfactant, and 30 g deionized water was added dropwise. Then, 11 g of a 7% sodium persulfate aqueous solution and 12 g of 7% sodium bisulfite were added dropwise, and the temperature in the reaction vessel was maintained at 70 ℃. The total addition time was 60 minutes. Then, 11 g of a 10% strength solution of t-butyl hydroperoxide and 12 g of 7% strength sodium bisulphite were added thereto, and the temperature in the reaction vessel was maintained at 65℃or higher for 45 minutes. Finally cooling to below 25 ℃, and then adjusting the pH to between 8 and 9 by ammonia water.
Example 3
100 G of deionized water is added at the bottom of a reaction kettle, 3 g of sodium dodecyl benzene sulfonate solution with the concentration of 25% is added after the reaction kettle is filled for a year, then 2 g of styrene-butadiene emulsion with the solid content of 50% is added, the Tg of the styrene-butadiene emulsion is-40 ℃, the dissolution rate is more than 80%, monomers which are respectively 70 g of isooctyl acrylate, 5g of methyl methacrylate, 1 g of hydroxyethyl acrylate and 1 g of acrylic acid are gradually added while stirring. After stirring for 30 minutes. The temperature is maintained at room temperature, typically between 25℃and 30 ℃. After the subsequent addition of nitrogen for 30 minutes, the addition of 0.4 g of a 70% solution of tert-butyl hydrogen peroxide and 6 g of sodium hydrogen sulfite at a concentration of 10% was started in one portion. The temperature was initially raised gradually to between 60 and 70 c with stirring, and then a mixture of monomers, 70 g butyl acrylate, 5g methyl methacrylate, 1 g hydroxyethyl acrylate, 1 g acrylic acid, 1 g sodium dodecyl benzene sulfonate as a 25% strength surfactant, and 30 g deionized water was added dropwise. Then, 11 g of a 7% sodium persulfate aqueous solution and 12 g of 7% sodium bisulfite were added dropwise, and the temperature in the reaction vessel was maintained at 70 ℃. The total addition time was 60 minutes. Then, 11 g of a 10% strength solution of t-butyl hydroperoxide and 12 g of 7% strength sodium bisulphite were added thereto, and the temperature in the reaction vessel was maintained at 65℃or higher for 45 minutes. Finally cooling to below 25 ℃, and then adjusting the pH to between 8 and 9 by ammonia water.
Comparative example 1
This control example is a conventional aqueous acrylic pressure sensitive adhesive (without addition of hinge monomer) preparation process.
150 G of water, 0.2 g of sodium dodecyl benzene sulfonate as a 25% surfactant, was placed at the bottom of the reactor, then heated to 85℃and 11 g of a 10% sodium persulfate solution was started to be added dropwise, after 5 minutes, a mixture of 140 g of butyl acrylate, 10 g of methyl methacrylate, 2 g of hydroxyethyl acrylate, 2 g of acrylic acid, 3g of a 25% sodium dodecyl benzene sulfonate solution as a surfactant and 52 g of deionized water was started to be added dropwise. The dripping time is 180 minutes, and the temperature in the reaction kettle is controlled at 85 ℃ during dripping. After the monomer was added dropwise, the temperature in the reaction vessel was maintained at 85 ℃. And held for 30 minutes. Then 1 g of 70% tertiary butyl hydrogen peroxide solution is added, then 12 g of 7% sodium bisulphite aqueous solution is added dropwise, the temperature in the reaction kettle is controlled to be more than 65 ℃ in the dropwise adding process, and the dropwise adding time is 60 minutes. Then ammonia water is added to adjust the pH value to 8-9 after the temperature of the whole reaction system is cooled to below 25 ℃.
Comparative example 2
The scheme is a preparation method of the traditional water-based pressure-sensitive adhesive (when the hinge monomer is added).
150 G of water, 0.2 g of sodium dodecyl benzene sulfonate as a surfactant with a concentration of 25%, are placed at the bottom of the reaction kettle, then the temperature is raised to 85 ℃,11 g of 10% sodium persulfate solution is started to be added dropwise, after 5 minutes, a mixture of 140 g of butyl acrylate, 10g of methyl methacrylate, 2g of hydroxyethyl acrylate, 2g of acrylic acid, 0.1% of 1, 4-butanediol diacrylate, 3g of 25% sodium dodecyl benzene sulfonate as a surfactant and 52g of deionized water is started to be added dropwise. The dripping time is 180 minutes, and the temperature in the reaction kettle is controlled at 85 ℃ during dripping. After the monomer was added dropwise, the temperature in the reaction vessel was maintained at 85 ℃. And held for 30 minutes. Then 1 g of 70% tertiary butyl hydrogen peroxide solution is added, then 12 g of 7% sodium bisulphite aqueous solution is added dropwise, the temperature in the reaction kettle is controlled to be more than 65 ℃ in the dropwise adding process, and the dropwise adding time is 60 minutes. Then adding ammonia water to adjust pH to 8-9 after the temperature of the whole reaction system is cooled to below 25 DEG C
The glues obtained in example 1, example 2, comparative example 1 and comparative example were coated on a 50 μm white PVC substrate, dried at 100℃for 3 minutes, and subjected to a table of coating weights, and then tested for various indexes of holding viscosity and peeling force, the initial adhesion ball method was carried out according to GB/T4852, holding viscosity was carried out according to GB/T4851-1998, and picture peeling force and 180-degree peeling force were measured according to GB/T2792-2014, and the results are shown in Table 1 below.
Table 1 room temperature standard steel plate test
As is clear from the data in comparative example 1 and comparative example 2 in the above tables, the conventional pressure-sensitive adhesive increases its cohesion (holding power) with the addition of the hinge monomer, but decreases its peeling force while improving the cohesion. As is clear from the comparison of the data of comparative example 1 and example 1, the cohesive force of the pressure-sensitive adhesive was effectively improved without decreasing the release force thereof after the addition of the styrene-butadiene emulsion.
The glues obtained in example 1, example 2, comparative example 1 and comparative example were coated on a 50 μm white PVC substrate, dried at 100℃for 3 minutes, and subjected to a table of gram weights, then aged in an oven for 3 days at 70℃and then cooled to room temperature after taking out, and then tested, the initial adhesion ball method was carried out according to GB/T4852, the holding adhesion was carried out according to GB/T4851-1998, and the picture peeling force and 180 degree peeling force were measured according to GB/T2792-2014, and the results are shown in Table 2 below.
TABLE 2 aging conditions 70 ℃ for 3 days, standard Steel plate test
As can be seen from the data in comparative examples 1 and 2 in the above table, after aging, the conventional pressure-sensitive adhesive maintains the cohesive force (holding viscosity) well and the corresponding peeling force has a certain ability of resisting the migration of the plasticizer due to the migration of the plasticizer in the PVC when the hinge monomer is added. As can be seen from the comparison of the data of comparative example 1 and example 1, the cohesion of the pressure-sensitive adhesive is well maintained after the addition of the styrene-butadiene emulsion, and the reduction of the peeling force is obviously superior to that of a pure acrylic pressure-sensitive adhesive system without the addition of the styrene-butadiene emulsion, so that the surface hybridization system can effectively improve the migration of the plasticizer.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but is intended to cover all equivalent modifications, direct or indirect, as would be included in the scope of the invention.
Claims (1)
1. The preparation method of the hybrid acrylic resin glue is characterized in that a preparation reaction system comprises deionized water, styrene-butadiene emulsion, acrylate monomers, a surfactant and an initiator, wherein the acrylate monomers comprise butyl acrylate, isooctyl acrylate, methyl methacrylate, hydroxyethyl acrylate and acrylic acid; the initiator is sodium persulfate or sodium bisulfite or tert-butyl hydroperoxide;
the mass ratio of butyl acrylate to isooctyl acrylate in the whole acrylate monomer component is 70% -90%;
the mass ratio of the styrene-butadiene emulsion to the acrylic ester monomer is 0.3: 1-0.5: 1, a step of;
the Tg of the styrene-butadiene emulsion is-40-0 ℃, and the dissolution rate is more than or equal to 80%;
The solid content of the styrene-butadiene emulsion is 45% -55%;
The pH of the mixture is adjusted to 8-9 after the reaction is completed;
The styrene-butadiene emulsion is added into deionized water, and then the acrylic ester monomer is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210858086.6A CN115215968B (en) | 2022-07-20 | 2022-07-20 | Preparation method of hybrid acrylic resin glue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210858086.6A CN115215968B (en) | 2022-07-20 | 2022-07-20 | Preparation method of hybrid acrylic resin glue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215968A CN115215968A (en) | 2022-10-21 |
| CN115215968B true CN115215968B (en) | 2024-04-26 |
Family
ID=83613572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210858086.6A Active CN115215968B (en) | 2022-07-20 | 2022-07-20 | Preparation method of hybrid acrylic resin glue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215968B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371470A (en) * | 2014-11-05 | 2015-02-25 | 广州福诚美化工有限公司 | Self-crosslinked water-based acrylic air-drying paint and preparation method thereof |
| CN104769069A (en) * | 2012-11-06 | 2015-07-08 | Lg化学株式会社 | Acryl-silicon based hybrid emulsion adhesive composition, and method for preparing same |
| CN111876105A (en) * | 2020-08-17 | 2020-11-03 | 山东京博中聚新材料有限公司 | Modified styrene-butadiene pressure-sensitive adhesive and preparation method thereof |
| KR20210145496A (en) * | 2020-05-25 | 2021-12-02 | 주식회사 엘지화학 | Acrylate based emulsion adhesive composition |
| CN114672256A (en) * | 2022-04-12 | 2022-06-28 | 广州市瑞得泰电工器材有限公司 | Emulsion pressure-sensitive adhesive and preparation method and application thereof |
-
2022
- 2022-07-20 CN CN202210858086.6A patent/CN115215968B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104769069A (en) * | 2012-11-06 | 2015-07-08 | Lg化学株式会社 | Acryl-silicon based hybrid emulsion adhesive composition, and method for preparing same |
| CN104371470A (en) * | 2014-11-05 | 2015-02-25 | 广州福诚美化工有限公司 | Self-crosslinked water-based acrylic air-drying paint and preparation method thereof |
| KR20210145496A (en) * | 2020-05-25 | 2021-12-02 | 주식회사 엘지화학 | Acrylate based emulsion adhesive composition |
| CN111876105A (en) * | 2020-08-17 | 2020-11-03 | 山东京博中聚新材料有限公司 | Modified styrene-butadiene pressure-sensitive adhesive and preparation method thereof |
| CN114672256A (en) * | 2022-04-12 | 2022-06-28 | 广州市瑞得泰电工器材有限公司 | Emulsion pressure-sensitive adhesive and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215968A (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100512358B1 (en) | BLENDS OF HIGH Tg POLYMER EMULSIONS AND PRESSURE SENSITIVE ADHESIVE POLYMER EMULSIONS USEFUL AS PRESSURE SENSITIVE ADHESIVES | |
| JP2925314B2 (en) | Pressure sensitive adhesives based on silicone emulsion | |
| US4500683A (en) | Pressure-sensitive adhesive composition | |
| JPS6356250B2 (en) | ||
| KR920000194B1 (en) | Structure reinforced latex particles and process for the preparation thereof | |
| CN111454402A (en) | Acrylate emulsion leather finishing agent and preparation method thereof | |
| JPS63196676A (en) | Pressure-sensitive adhesive | |
| CN115215968B (en) | Preparation method of hybrid acrylic resin glue | |
| US20030143409A1 (en) | Blends of high Tg polymer emulsions and pressure sensitive adhesive polymer emulsions useful as pressure sensitive adhesives | |
| CN108794682B (en) | Normal-temperature ketone hydrazine self-crosslinking acrylic resin emulsion and preparation method and application thereof | |
| CN118109148A (en) | High-solid-content solvent polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| US4742108A (en) | Structure reinforced latex particles | |
| US6747084B2 (en) | Process to prepare pressure-sensitive hybrid composite latex adhesives | |
| JPS5814474B2 (en) | Soft PVC molded body for pressure-sensitive adhesive | |
| JPS6369881A (en) | Aqueous pressure-sensitive adhesive composition | |
| JPH01221474A (en) | Pressure-sensitive adhesive composition | |
| JPH0586347A (en) | Adhesive | |
| JPS581712B2 (en) | Pressure sensitive adhesive composition for PVC | |
| JP3670362B2 (en) | Emulsion composition for adhesive and method for producing the same | |
| JPH01203412A (en) | Resin composition for tacky agent | |
| JPS59210917A (en) | Production of polychloroprene latex | |
| JPH0136512B2 (en) | ||
| CN115636898B (en) | Strippable acrylic emulsion, preparation method thereof and strippable protective film | |
| CN115287021B (en) | Waterproof Hou Shuixing acrylate pressure-sensitive adhesive and preparation method thereof | |
| JPS6334194B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |