CN1740257A - Prepn of water-base composite acrylic adhesive - Google Patents
Prepn of water-base composite acrylic adhesive Download PDFInfo
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- CN1740257A CN1740257A CN 200510103503 CN200510103503A CN1740257A CN 1740257 A CN1740257 A CN 1740257A CN 200510103503 CN200510103503 CN 200510103503 CN 200510103503 A CN200510103503 A CN 200510103503A CN 1740257 A CN1740257 A CN 1740257A
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Abstract
The water-base composite acrylic adhesive is prepared through first pre-emulsifying partial deionized water, partial emulsifier and partial reaction monomer to obtain the pre-emulsion I; pre-emulsifying the rest deionized water, emulsifier and reaction monomer to obtain the pre-emulsion II; adding partial initiator to the pre-emulsion II for emulsion polymerization to prepare seed, adding molecular weight regulator, dropping the pre-emulsion I, adding rest initiator, and controlling the pH value in the required range to complete the reaction and to obtain the water-base composite acrylic adhesive. The preparation process has low emulsifier consumption and stable emulsion reaction, and the product has high stability and high adhesion strength, and may be used in the adhesion of plastic film and aluminum film.
Description
Technical field
The invention belongs to the compound agent technical field that sticks with glue of food pack plastic film, relate in particular to a kind of preparation method of letex polymerization water soluble acrylic acid tackiness agent.
Background technology
All the time, food pack is compound to stick with glue agent and all adopts organic solvent adhesive, and it is all toxic to environment and human body.And aqueous composite adhesive is with water as solvent, and totally nontoxic is harmless, is a kind of environmental-protection type adhesive, is suitable for very much the compound of packaging material for food.The advantage of aqueous composite adhesive mainly contains: (1) laminated film does not have dissolvent residual, and wrapping material residual solvent foul smell reduces; (2) do not need solvent recovery unit, help the health of work situation in the factory; (3) there is not the danger of fire, blast; (4) cost is low.The acrylic emulsions tackiness agent is an aqueous adhesive relatively more commonly used, but the application of this aqueous adhesive at present is also very limited, its major cause is all too late solvent-based adhesive of the bonding strength of aqueous adhesive, all can more residual small-molecule substances in the aqueous adhesive, as emulsifying agent and other auxiliary agents, film forming can be separated out afterwards or to surface transport, influence the bonding of material surface; The surface tension of water is bigger in addition, causes the wettability of glue and film surface bad, also can influence bonding strength.Therefore, the bonding force of raising aqueous adhesive is the point of key.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who adopts the water soluble acrylic acid tackiness agent that stability is high, bonding strength is high of low soap emulsion polymerization prepared.
The technical solution used in the present invention is as follows:
The preparation method of water-base composite acrylic adhesive, it is characterized in that preparation process is: earlier part deionized water, partial emulsifier and partial reaction monomer are carried out pre-emulsification and obtain pre-emulsion I, residue deionized water, emulsifying agent and reaction monomers are carried out emulsification and are obtained emulsion II, add the part initiator and in emulsion II, carry out the emulsion polymerization prepared seed, begin to drip pre-emulsion I after adding molecular weight regulator again, and constantly additional remaining initiator, control pH value finishes to reacting in the acid number scope, obtains this water soluble acrylic acid tackiness agent.
The preparation method of described water-base composite acrylic adhesive is characterized in that the weight percent of described reaction monomers is:
Methyl acrylic ester 30～45%
Esters of acrylic acid 50～65%
(methyl) vinylformic acid 1～5%
Vinylformic acid hydroxyl ester class 1～5%
Described methyl acrylic ester monomer is that methyl methacrylate, Jia Jibingxisuanyizhi are or/and butyl methacrylate; Described acrylic ester monomer is that methyl acrylate, ethyl propenoate, butyl acrylate are or/and Isooctyl acrylate monomer; Described acrylic hydroxy ester monomer is that Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate are or/and Rocryl 410.Used (methyl) vinylformic acid can be methacrylic acid or vinylformic acid.
The concrete preparation process of this water-base composite acrylic adhesive is: with the deionized water of total amount 50～90%, 50～90% emulsifier for mixing emulsification, the mix monomer of otal investment 40～90% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 20～50% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
Described emulsifying agent is the mixture of alkyl naphthalene sulfonic acid sodium salt and two kinds of anionic emulsifier of Succinic Acid alkyl ester sulfonate sodium, and the two blended part by weight is 10: 1～10, and the consumption of emulsifying agent is 0.1～1.0% of a reaction monomers gross weight.
Described molecular weight regulator is a lauryl mercaptan, and consumption is 0.01～0.5% of a total monomer weight.
Letex polymerization all needs a certain amount of emulsifying agent to guarantee the stability of emulsion, but the existence of emulsifying agent has a negative impact to the adhesiveproperties of emulsion.The present invention adopts a kind of low soap emulsion polymerization, reduces the consumption of emulsifying agent under the prerequisite that guarantees emulsion-stabilizing as far as possible.The raising stability of emulsion of adopting new technology simultaneously, this novel process combines the advantage of traditional seeding polymerization method and pre-emulsion process, carry out seed earlier in the reaction starting stage, then that pre-emulsification is good emulsion slowly is added drop-wise to and continues reaction in the seed, rather than directly drip monomer, help stable the carrying out that reacts like this.The quality of pre-emulsifying effectiveness has a significant impact the stability of emulsion, flocculation material occurs after the emulsion that emulsification is bad will to be caused obtaining is placed for some time, serious layering directly occurs, and this has finally just influenced the adhesiveproperties of glue.
The effect of emulsifying agent is very important in the letex polymerization, and it not only influences the process of letex polymerization, also influences the adhesiveproperties of final emulsion.Two kinds of anionic emulsifier mixing uses have been used among the present invention, a kind of sodium alkyl naphthalene sulfonate salt (R-C that belongs to
10H
6-SO
3Na), R is the alkyl of 1～20 carbon atom here, for example isopropyl naphthalene sodium sulfonate, sodium butylnaphthalenesulfonate, dispersing agent MF etc.Another kind is succinic acid dialkyl ester sodium sulfonate salt [ROCOCH (ROCOCH
2)-SO
3Na], R is the alkyl of 1～20 carbon atom, for example diamyl succinate sodium sulfonate, succinate sodium 2-ethylhexyl, aerosol OT etc.After adopting blending emulsifiers, emulsifying effectiveness significantly improves, and can reduce the consumption of emulsifying agent greatly.This emulsifying agent consumption be chosen in amount of monomer 0.1～1% between.
The water-base composite acrylic adhesive of the present invention's preparation, its solids content is 30～60%, can be used in compound between packing such as PE (polyethylene)/PET (polyethylene terephthalate), BOPP (Biaxially oriented polypropylene film (BOPP))/CPP (cast polypropylene), BOPP/VMCPP (CPP aluminizes), BOPP/VMPET (aluminum plated PET) materials, stripping strength can reach more than the 1.0N/15mm, fully replace solvents type tackiness agent.
Effect of the present invention is, this preparation method adopts low soap method of emulsion polymerization, earlier partially polymerized monomer is carried out pre-emulsification another part monomer and prepare seed, effectively reduced the consumption of emulsifying agent, simultaneously in conjunction with seeding polymerization and pre-emulsified technology, use two kinds of negatively charged ion blending emulsifierss, the emulsion stable reaction, obtain the product stability height, the bonding strength height, can be used for compound between various plastic films or plastic film and the aluminium plating film, stripping strength all can reach more than the 1.0N/15mm, fully can replace solvents type tackiness agent on the food packing film Application of composite.
Embodiment:
Embodiment 1 gets the preparation raw material by following component and weight part:
Ethyl propenoate 41
Butyl acrylate 20
Methyl methacrylate 33
Butyl methacrylate 2.5
Vinylformic acid 2
Propylene glycol monoacrylate 1.5
Deionized water 150
Isopropyl naphthalene sodium sulfonate 0.3
Succinate sodium 2-ethylhexyl 0.1
(NH4)
2S
2O
8 0.6
NaHCO
3 0.25
Lauryl mercaptan 0.3
Synthetic method: with the deionized water of total amount 50%, 90% emulsifier for mixing emulsification, the mix monomer of otal investment 50% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 20% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
Testing method: adopt dry method compound, on common compounding machine, carry out the compound of structural membrane such as PE/PET, BOPP/CPP, BOPP/VMCPP, BOPP/VMPET.Be cut into 180 * 15mm strip then and test T type stripping strength on the electron detachment trier, test according to the GB/T2791-1995 standard, test result sees Table 1
Example 2 is got the preparation raw material by following component and weight part:
Butyl acrylate 50
Methyl acrylate 6
Methyl methacrylate 41
Methacrylic acid 1
Hydroxyethyl acrylate 2
Deionized water 120
Sodium butylnaphthalenesulfonate 0.25
Diamyl succinate sodium sulfonate 0.1
(NH4)
2S
2O
8 0.8
NaHCO
3 0.30
Lauryl mercaptan 0.25
Synthetic method is with example 1, and the product performance test result sees Table 1
Table 1
| Project | Composite structure | Stripping strength (N/15mm) |
| Example 1 | BOPP/VMCPP | 1.12 |
| BOPP/CPP | 1.63 | |
| BOPP/VMPET | 1.24 | |
| PE/PET | 1.78 | |
| Example 2 | BOPP/VMCPP | 1.03 |
| BOPP/CPP | 1.52 | |
| BOPP/VMPET | 1.20 | |
| PE/PET | 1.65 |
Example 3 is got the preparation raw material by following component and weight part:
Isooctyl acrylate monomer 40
Methyl acrylate 10
Butyl acrylate 10
Ethyl propenoate 5
Methyl methacrylate 30
Methacrylic acid 1
Hydroxyethyl methylacrylate 2
Propylene glycol monoacrylate 2
Deionized water 100
Dispersing agent MF 0.5
Succinate sodium 2-ethylhexyl 0.05
(NH4)
2S
2O
8 0.8
NaHCO
3 0.30
Lauryl mercaptan 0.5
Preparation method: with the deionized water of total amount 90%, 50% emulsifier for mixing emulsification, the mix monomer of otal investment 40% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 50% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
Embodiment 4 gets the preparation raw material by following component and weight part:
Butyl acrylate 50
Methyl methacrylate 30
Butyl methacrylate 10
Jia Jibingxisuanyizhi 5
Vinylformic acid 1
Propylene glycol monoacrylate 4
Deionized water 110
Isopropyl naphthalene sodium sulfonate 0.5
Aerosol OT 0.5
(NH4)
2S
2O
8 0.6
NaHCO
3 0.25
Lauryl mercaptan 0.01
Preparation method: with the deionized water of total amount 80%, 70% emulsifier for mixing emulsification, the mix monomer of otal investment 90% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 50% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
Embodiment 5 gets the preparation raw material by following component and weight part:
Isooctyl acrylate monomer 40
Methyl acrylate 10
Butyl acrylate 10
Ethyl propenoate 5
Methyl methacrylate 30
Methacrylic acid 1
Rocryl 410 4
Deionized water 100
Dispersing agent MF 0.5
Succinate sodium 2-ethylhexyl 0.05
(NH4)
2S
2O
8 0.8
NaHCO
3 0.30
Lauryl mercaptan 0.5
Preparation method: with the deionized water of total amount 90%, 50% emulsifier for mixing emulsification, the mix monomer of otal investment 40% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 50% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
Claims (5)
1. the preparation method of water-base composite acrylic adhesive, it is characterized in that preparation process is: earlier part deionized water, partial emulsifier and partial reaction monomer are carried out pre-emulsification and obtain pre-emulsion I, residue deionized water, emulsifying agent and reaction monomers are carried out emulsification and are obtained emulsion II, add the part initiator and in emulsion II, carry out the emulsion polymerization prepared seed, begin to drip pre-emulsion I after adding molecular weight regulator again, and constantly additional remaining initiator, control pH value finishes to reacting in the acid number scope, obtains this water soluble acrylic acid tackiness agent.
2. the preparation method of water-base composite acrylic adhesive according to claim 1 is characterized in that the weight percent of described reaction monomers is:
Methyl acrylic ester 30～45%
Esters of acrylic acid 50～65%
(methyl) vinylformic acid 1～5%
Vinylformic acid hydroxyl ester class 1～5%
Described methyl acrylic ester monomer is that methyl methacrylate, Jia Jibingxisuanyizhi are or/and butyl methacrylate; Described acrylic ester monomer is that methyl acrylate, ethyl propenoate, butyl acrylate are or/and Isooctyl acrylate monomer; Described acrylic hydroxy ester monomer is that Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate are or/and Rocryl 410.
3. the preparation method of water-base composite acrylic adhesive according to claim 1, it is characterized in that preparation process is: with the deionized water of total amount 50～90%, 50～90% emulsifier for mixing emulsification, the mix monomer of otal investment 40～90% carries out pre-emulsification and obtains pre-emulsion I, with remaining deionized water, emulsifying agent and reaction monomers are thrown into and are carried out emulsification in the polymeric kettle and obtain emulsion II, emulsion II is warming up to 70～75 ℃, the ammonium persulfate solution that adds total amount 20～50% carries out polyreaction, add molecular weight regulator behind reaction 20～30min and regulate molecular weight, begin to drip pre-emulsion I then, 3～4h dropwises, and constantly additional remaining ammonium persulfate solution, regulate the pH value between 3～5 with sodium hydrogen carbonate solution simultaneously, dropwise the back at 80～85 ℃ of insulation 1～2h, cooling to then and regulating the pH value with ammoniacal liquor below 50 ℃ is 6～7, obtains water-base composite acrylic adhesive.
4. according to the preparation method of claim 1 and 3 described water-base composite acrylic adhesives, it is characterized in that described emulsifying agent is the mixture of alkyl naphthalene sulfonic acid sodium salt and two kinds of anionic emulsifier of Succinic Acid alkyl ester sulfonate sodium, the two blended part by weight is 10: 1～10, and the consumption of emulsifying agent is 0.1～1.0% of a reaction monomers gross weight.
5. according to the preparation method of claim 1 and 3 described water-base composite acrylic adhesives, it is characterized in that described molecular weight regulator is a lauryl mercaptan, consumption is 0.01～0.5% of a total monomer weight.
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|---|---|---|---|
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|---|---|---|---|
| CNB2005101035032A CN100400612C (en) | 2005-09-19 | 2005-09-19 | Prepn of water-base composite acrylic adhesive |
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| CN100400612C CN100400612C (en) | 2008-07-09 |
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