CN111269350A - Environment-friendly water-based plastic-plastic composite adhesive and preparation method thereof - Google Patents
Environment-friendly water-based plastic-plastic composite adhesive and preparation method thereof Download PDFInfo
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- CN111269350A CN111269350A CN202010235601.6A CN202010235601A CN111269350A CN 111269350 A CN111269350 A CN 111269350A CN 202010235601 A CN202010235601 A CN 202010235601A CN 111269350 A CN111269350 A CN 111269350A
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
Abstract
The invention relates to an environment-friendly water-based plastic-plastic composite adhesive and a preparation method thereof, wherein the environment-friendly water-based plastic-plastic composite adhesive comprises styrene, butyl acrylate, isooctyl acrylate, acrylic acid, a cross-linking agent, an emulsifier, deionized water and an initiator, and the preparation method comprises S100 and emulsion preparation; s200, preparing seed emulsion; s300, dropwise adding and mixing; s400, eliminating and S500, adjusting PH and the like, and the prepared water-based plastic-plastic composite glue has high composite strength and water resistance and good film forming property.
Description
Technical Field
The invention belongs to the technical field of water-based pressure-sensitive adhesives, and particularly relates to an environment-friendly water-based plastic-plastic composite adhesive and a preparation method thereof.
Background
The plastic-plastic composite flexible package in China is mainly applied to aluminum-plastic composite and plastic-plastic composite, and the plastic-plastic composite glue for the plastic flexible package is widely applied to the fields of food, cosmetics, washing products and the like at present. The adhesive for producing the plastic-plastic composite film, namely the water-based composite adhesive takes water as a dispersion medium, has the characteristic of safe production and application, does not use an organic solvent, greatly reduces the emission of volatile organic compounds, further meets the requirements of the society on environmental protection, safety, health and the like, and has developed trend by replacing a solvent-based adhesive with high VOC emission with the water-based adhesive.
At present, most of plastic composite adhesives in the market are alcohol-soluble or solvent-soluble composite adhesives, but the composite adhesives are not environment-friendly enough, have general composite strength and water resistance, and have poor film forming property after crosslinking.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problems that the existing plastic composite adhesive is not environment-friendly enough, has general composite strength and water resistance and has poor film forming property after crosslinking.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to an environment-friendly water-based plastic-plastic composite adhesive, which comprises styrene, butyl acrylate, isooctyl acrylate, acrylic acid, a cross-linking agent, an emulsifier, deionized water and an initiator.
Preferably, the content of each component is as follows: 20-25 parts of styrene, 50-60 parts of butyl acrylate, 8-20 parts of isooctyl acrylate, 0.5-5 parts of acrylic acid, 1-5 parts of a cross-linking agent, 0.3-2.5 parts of an emulsifier and 0.1-0.7 part of an initiator.
Preferably, the crosslinking agent is at least one of acetoacetoxyethyl methacrylate, glycidyl methacrylate and N-isobutoxy acrylamide.
Preferably, the initiator is at least one of sodium persulfate, ammonium persulfate and potassium persulfate.
Preferably, the emulsifier comprises an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is 0.2-1.2 parts by weight, and the nonionic emulsifier is 0.1-1 part by weight.
Preferably, the anionic emulsifier is at least one of ethoxylated sodium alkyl sulfate, sodium alkyl ether sulfate, sodium fatty alcohol ether sulfate and polyoxyethylene ether sulfate.
Preferably, the nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and allyloxy polyoxyethylene ether.
The preparation method of the environment-friendly water-based plastic-plastic composite adhesive is characterized by comprising the following steps of:
s100, preparing an emulsion, fully stirring and mixing all the emulsifier and 25-35% of deionized water for 15-30 minutes, adding styrene, butyl acrylate, isooctyl acrylate, acrylic acid and a cross-linking agent, and then continuously stirring and emulsifying for 30-60 minutes to prepare the emulsion;
s200, preparing a seed emulsion, adding 50-65% of deionized water into a reaction kettle, heating, adding 3-7% of the emulsion prepared in S100 at 80-90 ℃, simultaneously adding 60-70% of an initiator solution, and reacting for 15-30 minutes to prepare the seed emulsion;
s300, dropwise adding and mixing, dropwise adding the rest emulsion and the initiator solution into the prepared seed emulsion at a constant speed for 3-4 hours, wherein the temperature in the dropwise adding process is 80-90 ℃;
s400, performing post-elimination, dropwise adding the mixed emulsion, performing heat preservation reaction for 1-2 hours, cooling to 72 ℃, performing post-elimination, performing heat preservation reaction for 1 hour after the post-elimination is finished, wherein the reason that the initiation rate of tert-butyl hydroperoxide and a reducing agent FF6M at 72 ℃ is high is that the residual monomer content in the system can be quickly eliminated at 72 ℃;
s500, adjusting the pH value, cooling the emulsion after heat preservation to below 40 ℃, adding ammonia water to adjust the pH value of the product to 7-8, and filtering the mixture to obtain the aqueous plastic-plastic composite glue.
Preferably, the post-elimination in step S400 is to weigh 1 to 3% of deionized water, dissolve the oxidant tert-butyl hydroperoxide, prepare a post-elimination oxidant aqueous solution, weigh 1 to 3% of deionized water, dissolve the reductant FF6M, prepare a post-elimination reductant aqueous solution, cool to 72 ℃, drop the prepared post-elimination oxidant aqueous solution, keep an interval of 10 minutes after dropping, eliminate the reductant aqueous solution after dropping, and perform a heat preservation reaction for 1 hour after dropping.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the invention relates to an environment-friendly water-based plastic-plastic composite adhesive and a preparation method thereof, wherein the environment-friendly water-based plastic-plastic composite adhesive comprises styrene, butyl acrylate, isooctyl acrylate, acrylic acid, a cross-linking agent, an emulsifier, deionized water and an initiator, and the preparation method comprises S100 and emulsion preparation; s200, preparing seed emulsion; s300, dropwise adding and mixing; s400, eliminating and S500, adjusting PH and the like, and the prepared water-based plastic-plastic composite glue has high composite strength and water resistance and good film forming property.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings, in which several embodiments of the invention are shown, but which may be embodied in many different forms and are not limited to the embodiments described herein, but rather are provided for the purpose of providing a more thorough disclosure of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
Referring to fig. 1, the environment-friendly water-based plastic-plastic composite adhesive of the embodiment includes styrene, butyl acrylate, isooctyl acrylate, acrylic acid, a cross-linking agent, an emulsifier, deionized water and an initiator.
Wherein the content of each component is as follows: 20-25 parts of styrene, 50-60 parts of butyl acrylate, 8-20 parts of isooctyl acrylate, 0.5-5 parts of acrylic acid, 1-5 parts of a cross-linking agent, 0.3-2.5 parts of an emulsifier and 0.1-0.7 part of an initiator.
Wherein the crosslinking agent is at least one of acetoacetoxyethyl methacrylate, glycidyl methacrylate and N-isobutoxy acrylamide.
Wherein the initiator is at least one of sodium persulfate, ammonium persulfate and potassium persulfate.
The emulsifier comprises an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is 0.2-1.2 parts by weight, and the nonionic emulsifier is 0.1-1 part by weight.
Wherein the anionic emulsifier is at least one of ethoxylated alkyl sodium sulfate, alkyl ether sodium sulfate, fatty alcohol ether sodium sulfate and polyoxyethylene ether sodium sulfate.
Wherein the nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and allyloxy polyoxyethylene ether.
A preparation method of environment-friendly water-based plastic-plastic composite glue comprises the following steps:
s100, preparing an emulsion, fully stirring and mixing all the emulsifier and 25-35% of deionized water for 15-30 minutes, adding styrene, butyl acrylate, isooctyl acrylate, acrylic acid and a cross-linking agent, and then continuously stirring and emulsifying for 30-60 minutes to prepare the emulsion;
s200, preparing a seed emulsion, adding 50-65% of deionized water into a reaction kettle, heating, adding 3-7% of the emulsion prepared in S100 at 80-90 ℃, simultaneously adding 60-70% of an initiator solution, and reacting for 15-30 minutes to prepare the seed emulsion;
s300, dropwise adding and mixing, dropwise adding the rest emulsion and the initiator solution into the prepared seed emulsion at a constant speed for 3-4 hours, wherein the temperature in the dropwise adding process is 80-90 ℃, if the temperature is lower than 80 ℃, the reaction temperature is too low, and the initiator does not reach the optimal initiation reaction temperature, so that the polymerization speed is very slow, the reaction time is too long, the monomer conversion rate is low, and the performance of the synthesized plastic-plastic composite emulsion is poor; if the temperature is higher than 90 ℃, the reaction temperature is too high, the initiation reaction of the initiator is too fast, the polymerization reaction is too violent and is difficult to control, implosion and gel phenomena can occur, and the performance of the emulsion is influenced. In addition, the particle size, molecular weight and distribution of the emulsion are also influenced by the reaction temperature;
s400, then eliminating, dropwise adding the mixed emulsion, performing heat preservation reaction for 1-2 hours, cooling to 72 ℃, then eliminating, and performing heat preservation reaction for 1 hour after the elimination is finished;
s500, adjusting the pH value, cooling the emulsion after heat preservation to below 40 ℃, adding ammonia water to adjust the pH value of the product to 7-8, and filtering the mixture to obtain the aqueous plastic-plastic composite glue.
The post-elimination in the step S400 is to weigh 1-3% of deionized water, dissolve an oxidant tert-butyl hydroperoxide to prepare a post-elimination oxidant aqueous solution, weigh 1-3% of deionized water, dissolve a reducing agent FF6M, and prepare a post-elimination reducing agent aqueous solution; cooling to 72 ℃, dropwise adding the prepared post-elimination oxidant aqueous solution, carrying out the interval of 10 minutes after dropwise adding, eliminating the reducing agent aqueous solution after dropwise adding, and carrying out heat preservation reaction for 1 hour after adding.
The specific components and processes of this example are as follows:
s100, weighing 16g of deionized water, 0.4g of sodium alkyl ether sulfate and 0.2g of fatty alcohol polyoxyethylene ether, stirring for 15 minutes at normal temperature, adding 8g of styrene, 4g of isooctyl acrylate, 26g of butyl acrylate, 0.8g of acrylic acid and 1.2g of acetoacetoxyethyl methacrylate, and quickly stirring for 30 minutes to obtain the emulsion.
S200, weighing 0.15g of ammonium persulfate, and dissolving with 1g of deionized water to prepare an initiator solution A; weighing 0.1g of ammonium persulfate, dissolving with 3g of deionized water to prepare an initiator solution B, weighing 36g of deionized water, adding into a reaction kettle, heating to raise the temperature until the temperature is stabilized at 85 ℃, and adding 3% of emulsion;
s300, adding the initiator solution A prepared in the step S200, reacting for 15 minutes, beginning to dropwise add the rest emulsion and the initiator solution B prepared in the step c at a constant speed for 3 hours, controlling the reaction temperature at 80-90 ℃, and preserving heat for 1 hour after dropwise adding;
s400, cooling to 72 ℃, performing post-treatment, weighing 0.10g of tert-butyl hydroperoxide, dissolving with 1g of deionized water, adding into a reaction kettle at an interval of 10 minutes, weighing 0.05gFF6M, dissolving with 1g of deionized water, adding into the reaction kettle, and after the elimination, performing heat preservation reaction for 1 hour
S500, cooling to below 40 ℃, weighing 1g of ammonia water, adding the ammonia water into the reaction kettle, uniformly stirring, filtering with 200-mesh filter cloth, and discharging to obtain the aqueous environment-friendly plastic-plastic composite rubber product.
The application comprises the following steps: coating the prepared composite adhesive emulsion on a PE film, wherein the amount of the adhesive per square dry is about 2g, the composite pressure is 4-5kg, the drying temperature is 50-70 ℃, the drying time is 30 seconds, after the composite film is placed for 10 minutes at normal temperature, the composite film is placed in a water bath at 60 ℃ for soaking for 3 hours, the composite adhesive layer is not whitened, and the composite film cannot be torn.
Example 2
The specific components and processes of this example are as follows:
s100, emulsifying cylinder materials, weighing 100g of deionized water, 1.91g of fatty alcohol ether sulfate sodium salt and 1.36g of fatty alcohol polyoxyethylene ether, stirring for 15 minutes at normal temperature, adding 45g of styrene, 23g of acrylate isooctyl ester, 118.1g of butyl acrylate, 5.0g of acrylic acid and 3.9g of glycidyl methacrylate, and quickly stirring for 30 minutes to obtain an emulsion.
S200, weighing 0.63g of ammonium persulfate, and dissolving with 10g of deionized water to prepare an initiator solution A; weighing 0.35g of ammonium persulfate, dissolving with 20g of deionized water to prepare an initiator solution B, weighing 150g of deionized water, adding into a reaction kettle, heating to raise the temperature until the temperature is stabilized at 85 ℃, and adding 3% of emulsion;
s300, adding the initiator solution A prepared in the step S200, reacting for 20 minutes, beginning to dropwise add the rest emulsion and the initiator solution B prepared in the step c at a constant speed for 3 hours, controlling the reaction temperature to be 80-90 ℃, and preserving heat for 1 hour after dropwise adding;
s400, cooling to 72 ℃, performing post-treatment, weighing 0.5g of tert-butyl hydroperoxide, dissolving with 7.5g of deionized water, adding into a reaction kettle at an interval of 10 minutes, weighing 0.25gFF6M, dissolving with 7.5g of deionized water, adding into the reaction kettle, and after the elimination, performing heat preservation reaction for 1 hour;
s500, cooling to below 40 ℃, weighing 5g of ammonia water, adding the ammonia water into the reaction kettle, uniformly stirring, filtering with 200-mesh filter cloth, and discharging to obtain the aqueous environment-friendly plastic-plastic composite rubber product.
The application comprises the following steps: coating the prepared composite adhesive emulsion on a PE film, wherein the amount of the adhesive per square dry is about 2g, the composite pressure is 4-5kg, the drying temperature is 50-70 ℃, the drying time is 30 seconds, after the composite film is placed for 10 minutes at normal temperature, the composite film is placed in a water bath at 60 ℃ for soaking for 3 hours, the composite adhesive layer is not whitened, and the composite film cannot be torn.
Example 3
S100, emulsifying cylinder materials, weighing 150g of deionized water, 4.0g of fatty alcohol ether sulfate sodium salt and 2.4g of isomeric tridecanol polyoxyethylene ether, stirring for 15 minutes at normal temperature, adding 100g of styrene, 60g of acrylate isooctyl ester, 211g of butyl acrylate, 9.0g of acrylic acid and 20g of acetoacetoxyethyl methacrylate, and quickly stirring for 30 minutes to prepare an emulsion;
s200, weighing 1.44g of ammonium persulfate, and dissolving with 15g of deionized water to prepare an initiator solution A; weighing 0.96g of ammonium persulfate, and dissolving the ammonium persulfate by using 30g of deionized water to prepare an initiator solution B; 366g of deionized water is weighed and added into a reaction kettle, and after the temperature is raised to 85 ℃, 3 percent of emulsion is added;
s300, adding the initiator solution A prepared in the S200, reacting for 20 minutes, beginning to dropwise add the rest emulsion and the initiator solution B prepared in the step c at a constant speed for 3 hours, controlling the reaction temperature at 80-90 ℃, and preserving heat for 1 hour after dropwise adding;
s400, cooling to 72 ℃, performing post-treatment, weighing 0.8g of tert-butyl hydroperoxide, dissolving with 10g of deionized water, adding into a reaction kettle at an interval of 10 minutes, weighing 0.4gFF6M, dissolving with 10g of deionized water, adding into the reaction kettle, and after the elimination, performing heat preservation reaction for 1 hour;
s500, cooling to below 40 ℃, weighing 9g of ammonia water, adding the ammonia water into the reaction kettle, uniformly stirring, filtering with 200-mesh filter cloth, and discharging to obtain the aqueous environment-friendly plastic-plastic composite rubber product.
The application comprises the following steps: coating the prepared composite adhesive emulsion on a PE film, wherein the amount of the adhesive per square dry is about 2g, the composite pressure is 4-5kg, the drying temperature is 50-70 ℃, the drying time is 30 seconds, after the composite film is placed for 10 minutes at normal temperature, the composite film is placed in a water bath at 60 ℃ for soaking for 3 hours, the composite adhesive layer is not whitened, and the composite film cannot be torn.
The above-mentioned embodiments only express a certain implementation mode of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention; it should be noted that, for those skilled in the art, without departing from the concept of the present invention, several variations and modifications can be made, which are within the protection scope of the present invention; therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The environment-friendly water-based plastic-plastic composite adhesive is characterized in that: comprises styrene, butyl acrylate, isooctyl acrylate, acrylic acid, a cross-linking agent, an emulsifier, deionized water and an initiator.
2. The environment-friendly water-based plastic-plastic composite adhesive as claimed in claim 1, wherein the contents of the components are as follows: 20-25 parts of styrene, 50-60 parts of butyl acrylate, 8-20 parts of isooctyl acrylate, 0.5-5 parts of acrylic acid, 1-5 parts of a cross-linking agent, 0.3-2.5 parts of an emulsifier and 0.1-0.7 part of an initiator.
3. The environment-friendly water-based plastic-plastic composite adhesive as claimed in claim 2, wherein: the crosslinking agent is specifically at least one of acetoacetoxy ethyl methacrylate, glycidyl methacrylate and N-isobutoxy acrylamide.
4. The environment-friendly water-based plastic-plastic composite adhesive as claimed in claim 2, wherein: the initiator is at least one of sodium persulfate, ammonium persulfate and potassium persulfate.
5. The environment-friendly water-based plastic-plastic composite adhesive as claimed in claim 2, wherein: the emulsifier comprises an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is 0.2-1.2 parts by weight, and the nonionic emulsifier is 0.1-1 part by weight.
6. The environment-friendly water-based plastic composite glue as claimed in claim 5, wherein: the anionic emulsifier is at least one of ethoxylated alkyl sodium sulfate, alkyl ether sodium sulfate, fatty alcohol ether sodium sulfate and polyoxyethylene ether sulfate.
7. The environment-friendly water-based plastic composite glue as claimed in claim 5, wherein: the nonionic emulsifier is at least one of fatty alcohol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and allyloxy polyoxyethylene ether.
8. The preparation method of the environment-friendly water-based plastic composite glue according to any one of claims 1 to 7, characterized by comprising the following steps:
s100, preparing an emulsion, fully stirring and mixing all the emulsifier and 25-35% of deionized water for 15-30 minutes, adding styrene, butyl acrylate, isooctyl acrylate, acrylic acid and a cross-linking agent, and then continuously stirring and emulsifying for 30-60 minutes to prepare the emulsion;
s200, preparing a seed emulsion, adding 50-65% of deionized water into a reaction kettle, heating, adding 3-7% of the emulsion prepared in S100 at 80-90 ℃, simultaneously adding 60-70% of an initiator solution, and reacting for 15-30 minutes to prepare the seed emulsion;
s300, dropwise adding and mixing, dropwise adding the rest emulsion and the initiator solution into the prepared seed emulsion at a constant speed for 3-4 hours, wherein the temperature in the dropwise adding process is 80-90 ℃;
s400, then eliminating, dropwise adding the mixed emulsion, performing heat preservation reaction for 1-2 hours, cooling to 72 ℃, then eliminating, and performing heat preservation reaction for 1 hour after the elimination is finished;
s500, adjusting the pH value, cooling the emulsion after heat preservation to below 40 ℃, adding ammonia water to adjust the pH value of the product to 7-8, and filtering the mixture to obtain the aqueous plastic-plastic composite glue.
9. The preparation method of the environment-friendly water-based plastic-plastic composite glue according to claim 8, characterized by comprising the following steps: the post-elimination in the step S400 is to weigh 1-3% of deionized water, dissolve the oxidant tert-butyl hydroperoxide to prepare a post-elimination oxidant aqueous solution, weigh 1-3% of deionized water, dissolve the reducing agent FF6M to prepare a post-elimination reducing agent aqueous solution; cooling to 72 ℃, dropwise adding the prepared post-elimination oxidant aqueous solution, carrying out the interval of 10 minutes after dropwise adding, eliminating the reducing agent aqueous solution after dropwise adding, and carrying out heat preservation reaction for 1 hour after adding.
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Application publication date: 20200612 |