CN112094618A - Adhesive for soft package compounding and preparation method thereof - Google Patents
Adhesive for soft package compounding and preparation method thereof Download PDFInfo
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- CN112094618A CN112094618A CN202011018246.3A CN202011018246A CN112094618A CN 112094618 A CN112094618 A CN 112094618A CN 202011018246 A CN202011018246 A CN 202011018246A CN 112094618 A CN112094618 A CN 112094618A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a binder for soft package compounding and a preparation method thereof, belonging to the field of polymer fine chemical synthesis and application. An adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, a chain extender B3 and a leveling assistant B4, wherein the polyether polyol A1 mainly comprises difunctional polyol and trifunctional polyol which take PO as a polymerization monomer, the molecular weight of the difunctional polyol and the trifunctional polyol is 300-5000, and the vegetable oil polyol A2 specifically adopts any one of soybean oil polyol, palm oil polyol and castor oil polyol; the double-component solvent-free polyurethane adhesive disclosed by the invention not only meets the detection standard, but also has a better obvious effect, and can well maintain the quality of a product.
Description
Technical Field
The invention relates to the technical field of high-molecular fine chemical synthesis and application, in particular to a binder for flexible package compounding and a preparation method thereof.
Background
With the progress of economy and food industry in China, people's life is greatly improved, and consumers prefer cooked food which is rich in nutrition and convenient to eat. The packaging of most raw meat and cooked meat products in China can be polluted by light, moisture, oxygen and microorganisms in the storage and transportation processes, so that the shelf life is shortened, and even the food safety problem is caused, therefore, how to better maintain the good quality states of the meat products and the like, prevent the spoilage of the meat products, build a more convenient consumption mode is a big problem faced by the current meat product production enterprises, the proper packaging material is favorable for maintaining the quality of the products, the transportation and the sale of the products are convenient, and the packaging method is a feasible scheme for solving the problems; the single-layer plastic film for early packaging, such as a polyethylene film, has high oxygen transmission rate of partial materials, low water vapor barrier property, no abrasion and puncture resistance and influences the quality of meat products.
On the other hand, people pay more attention to how to maintain the original attributes of foods and medicines, particularly to how to guarantee consumers to buy foods with original taste and flavor and how to prolong the validity period and the like of fast-food products. Therefore, more and more color printing factories develop barrier structures with different structures, such as PET/VMPET/PE, PET/VMCPP, PET/PA/PE, PET/AL/PE and the like, multiple effects of the packaging material can be realized through the composite application of high barrier materials, such as printability, attractiveness, moisture and vapor resistance, oxygen permeation resistance and packaging, the compounding among different materials can be realized through the bonding modes of co-extrusion bonding, dry compounding, wet compounding and the like, the co-extrusion compounding bonding strength is high, but the equipment investment cost is high, and the operation is complex; both dry lamination and wet lamination are realized by bonding two different materials by using an adhesive to form a composite structure of 'film/adhesive layer/film'. The dry compounding or the wet compounding has obvious defects, the dry compounding contains a large amount of solvent, a large amount of VOC gas is discharged during production, and the method is neither environment-friendly nor efficient; the wet composite has limited application structure, the drying of the moisture in the using process is a difficult-to-control process, the wet composite is only used for the structure with a 'perforated film' on at least one side so as to be convenient for the release of the moisture, and the processing machine speed is not very high, so the wet composite is not suitable for the compounding of double-barrier materials.
At present, more and more color printing factories use a novel solvent-free composite technology, which not only eliminates the existence of solvent VOC from the source, but also saves 1/2-1/3 compared with dry-type composite, on the other hand, the processing efficiency is obviously improved, and the machine speed of 350-, The direct compounding of more than two layers of high-barrier materials such as PET/PA/AL/PE is not widely used or mentioned.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an adhesive for soft package compounding and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
Preferably, the polyether polyol A1 is mainly a difunctional polyol and a trifunctional polyol which take PO as a polymerization monomer, and has the molecular weight of 300-5000.
Preferably, the vegetable oil polyol a2 is any one of soybean oil polyol, palm oil polyol and castor oil polyol.
Preferably, the isocyanate A3 is specifically one of TDI, IPDI, PAPI, MDI and NDI, and the isocyanate a4 is specifically modified isocyanate modified by carbodiimide or uretonimine.
Preferably, the chain extender B3 is any one of low molecular weight diol/amine, triol/amine, pentaerythritol, sucrose alcohol and maltitol.
Preferably, the leveling aid B4 is one or a mixture of two of an acrylate polymer and a silicone polymer.
Preferably, the adhesive enables direct composite lamination of two or more layers of high barrier materials.
A preparation method of an adhesive for flexible package composition comprises the following operation steps:
s1, preparing a main agent;
s2, preparing a curing agent;
s3, uniformly mixing the prepared main agent and the curing agent through a static mixing pipe at the temperature of 35-45 ℃ according to the mass ratio of 100: 60-70;
s4, compounding the membrane material on a solvent-free coating machine;
s5, the compounded laminated film is suspended in a drying room at 40-45 ℃ to be cured for 7-12 hours, and then sampling is carried out for detection and analysis.
Preferably, the step of preparing the main agent in step S1 is:
a. adding polyether polyol A1 or vegetable oil polyol A2 or a mixture of the two, wherein the water content of the polyether polyol A1 or the vegetable oil polyol A2 is lower than 0.05 percent, into a three-port reaction kettle;
b. stirring and heating to 50 ℃, adding isocyanate A3, and then reacting for several hours at constant temperature of 55-65 ℃;
c. adding isocyanate A4, and continuing to react at constant temperature;
d. placing under-0.1 MPa for vacuum defoaming for 30-45 min;
e. filtering and discharging to obtain the main agent.
Preferably, the step of preparing the curing agent in step S2 is:
a. adding polyether polyol B1, polyol B2, a chain extender B3 and a leveling assistant B4 into a three-port reaction kettle;
b. mixing, stirring and heating to 40-60 ℃;
c. placing under-0.1 MPa for vacuum defoaming for 60-90 min;
d. filtering and discharging to obtain the curing agent.
Compared with the prior art, the invention provides the adhesive for compounding the flexible package and the preparation method thereof, and the adhesive has the following beneficial effects:
1. the adhesive for compounding the flexible package can realize the compounding of non-high barrier materials by using a solvent-free adhesive for processing; the composite mode of the high-barrier material can be realized by processing the high-barrier material by a solvent-free adhesive; the direct composite lamination of more than two layers of high-barrier structures can be realized; the composition of at least the following common high-barrier structures can be realized: PET/PE, PET/AL, PET/PA, PA/AL, PET/EVOH, PET/PVDC, PET/VMPET, PET/VMCPP, PET/AL/PA/PE, PA/PE; high-speed operation in the composite processing process of more than two layers of high-barrier materials can be realized, and the processing speed of 120-200m/min is achieved; the composite high-efficiency energy-saving flexible packaging structure can be realized, the processing speed of the general structure can reach 350-plus-500 m/min, and the processing speed of the high-barrier structure can reach 120-plus-200 m/min.
2. The preparation method of the adhesive for the flexible package compounding comprises the following steps of curing the adhesive at the temperature of 35-45 ℃ for 7-10 hours; and the viscosity of the binder at 25 ℃ is respectively: the main agent is 2000-3500mPa.s, and the curing agent is 450-700 mPa.s; when the binder is constructed at the temperature of 35-45 ℃, the reaction rate viscosity is as follows: 1000-1900mpa.s at 15 min; 30 min: 3500-6500 mpa.s; 8000-15000mpa.s at 45 min; secondly, the binder adopts lower preparation temperature, the process steps are simple, the preparation temperature is only 50-65 ℃, no hazardous chemical component exists, the solid content is 100%, and the environmental protection safety laws and regulations are completely met; the mixture ratio is as follows: the main agent is a curing agent which is 100:50-70, and the optimal general mixture ratio is as follows: the main agent is a curing agent which is 100:60-70, and when the double-barrier lamination is compounded, the optimal mixture ratio is as follows: the main agent is a curing agent which is 100:70, the ratio of NCO groups in the main agent to active groups in the curing agent is 1.01-1.65, and the proportion of polymer polyol in the main agent before reaction is 30-60%, most preferably 35-45%; isocyanate A3 in a ratio of 30 to 50%, most preferably 35 to 45%; the proportion of the isocyanate A4 is 5-25%, most preferably 12-20%, and the adhesion force of the invention to the inner layer of an aluminum or plastic structure can reach 10N/15 mm.
3. The polyether polyol A1 is mainly di-functionality polyol and tri-functionality polyol which take PO as a polymerization monomer, the molecular weight is preferably 300-5000, and most preferably 400-2000, and the polyether polyol A1 can provide excellent adhesive force, low viscosity and water resistance; the polyether polyol A1 has easily controlled molecular weight, narrower distribution index, stable structure of the synthesized high polymer resin and high process controllability; the vegetable oil polyol A2 can be soybean oil polyol, palm oil polyol and castor oil polyol, and can also be vegetable oil polyol prepared by chemically modifying the above polyols, such as modified vegetable oil polyol prepared by alcoholysis reaction or ester exchange reaction, the vegetable oil polyol ester A2 can realize the purpose of rapid degradation and cyclic utilization, and the raw materials have wide sources, meanwhile, the vegetable oil polyol A2 has excellent cohesiveness, low temperature resistance and water resistance, the isocyanate A3 and the isocyanate A4 can be obtained from commercial channels, wherein the isocyanate A3 can be TDI, IPDI, PAPI, MDI and NDI, and 2-functionality liquid isocyanate is generally preferred; isocyanate a4 modified isocyanate modified by carbodiimide or uretonimine; polyether polyol B1 and polyol B2 are polymer polyols with EO or PO as polymerization monomers, wherein polyol B2 is a modified polymer polyol containing a small amount of-SH groups or-NH 2 groups, and polyether polyol B1 can also be vegetable oil polyol A2; the molecular weights of polymer polyol B1 and polyol B2 are selected to be 300-3000, and most preferably 350-1500; chain extender B3 is low molecular weight dihydric alcohol/amine, trihydric alcohol/amine and micromolecular polyhydric alcohol with tetrafunctionality higher than tetrafunctional degree, such as pentaerythritol, sucrose alcohol, maltitol, etc., preferably dihydric alcohol/amine and trihydric alcohol/amine, such as ethylene glycol, ethylenediamine, glycerol and triethanolamine; the leveling assistant B4 is mainly acrylate high molecular polymer or organosilicon high molecular polymer used alone or in combination; the proportion of the polymer polyol in the main agent before reaction is 30-60%, and the most preferable proportion is 35-45%; isocyanate A3 in a ratio of 30 to 50%, most preferably 35 to 45%; 5-25% of isocyanate A4, most preferably 12-20%; the polymer is blocked by isocyanate groups, so that no hydroxyl group exists, and the storage stability of the product is ensured.
The parts which are not involved in the invention are the same as the prior art or can be realized by the prior art, and the double-component solvent-free polyurethane adhesive not only meets the detection standard, but also has better obvious effect and can well maintain the quality of the product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example 1:
an adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
The preparation method of the main agent comprises the following steps: a. 130 parts of polyether polyol A with the molecular weight of 2000, 15 parts of polyether polyol A with the molecular weight of 450 and 10 parts of polyol with the molecular weight of 1000 are added into a three-port reaction kettle; b. heating and stirring, adding MDI-5050 part when the temperature reaches 50 ℃, and then reacting for 2 hours at constant temperature of 60 ℃; c. adding 5 parts of MDI-100LL, and continuing to react for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. adding 180 parts of polyether polyol B with the molecular weight of 1000, 210 parts of polyol B with the molecular weight of 500, 10 parts of chain extender B3 diethylene glycol and leveling aid B4 into another clean three-neck flask; b, mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 90min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
Example 2:
an adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
The preparation method of the main agent comprises the following steps: a. 124 parts of polyether polyol A with the molecular weight of 2000, 13 parts of polyether polyol A with the molecular weight of 400 and 9 parts of polyol with the molecular weight of 1000 are added into a three-port reaction kettle; b. heating and heating, stirring, adding MDI-5044 parts when the temperature reaches 50 ℃, and then reacting for 2 hours at the constant temperature of 60 ℃; c. adding 20 parts of MDI-100LL, and continuously reacting for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. taking another clean three-neck flask, and adding 180 parts of polyether polyol B with the molecular weight of 1000, 215 parts of polyol B with the molecular weight of 500 and 5 parts of chain extender B3 glycerol; b. mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 80min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
Example 3:
an adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
The preparation method of the main agent comprises the following steps: a. adding 125 parts of polyether polyol A with the molecular weight of 2000, 3 parts of polyol with the molecular weight of 350 and 10 parts of polyol with the molecular weight of 1000 into a three-port reaction kettle; b. heating and heating, stirring, adding MDI-5047 parts when the temperature reaches 50 ℃, and then reacting for 2 hours at the constant temperature of 60 ℃; c. adding 15 parts of MDI-100LL, and continuing to react for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. adding 190 parts of polyether polyol B with the molecular weight of 1000, 25 parts of polyether polyol B with the molecular weight of 400, 5 parts of chain extender B3 diethylene glycol and a leveling assistant B4 into another clean three-neck flask; b. mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 90min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
Example 4:
an adhesive for flexible package compounding, comprising a main agent blocked with an isocyanate group and a curing agent blocked with a hydroxyl group, the main agent mainly comprising the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
The preparation method of the main agent comprises the following steps: a. adding 125 parts of polyether polyol A with the molecular weight of 2000, 15 parts of polyether polyol A with the molecular weight of 400 and 10 parts of polyol with the molecular weight of 1000 into a three-port reaction kettle; b. heating and heating, stirring, adding MDI-5042 parts when the temperature reaches 50 ℃, and then reacting for 2 hours at the constant temperature of 60 ℃; c. adding 18 parts of MDI-100LL, and continuously reacting for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. adding 280 parts of vegetable oil polyol A with the molecular weight of 1000, 210 parts of polyol B with the molecular weight of 450 and 10 parts of chain extender B3 diethylene glycol into another clean three-neck flask; b. mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 60min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
The polyether polyol A1 is mainly di-functionality polyol and tri-functionality polyol with PO as a polymerization monomer, the molecular weight is preferably 300-5000, and most preferably 400-2000, and the polyether polyol A1 can provide excellent adhesive force, low viscosity and water resistance; the polyether polyol A1 has easily controlled molecular weight, narrower distribution index, stable structure of the synthesized high polymer resin and high process controllability; the vegetable oil polyol A2 can be soybean oil polyol, palm oil polyol and castor oil polyol, and can also be vegetable oil polyol prepared by chemically modifying the above polyols, such as modified vegetable oil polyol prepared by alcoholysis reaction or ester exchange reaction, the vegetable oil polyol ester A2 can realize the purpose of rapid degradation and cyclic utilization, and the raw materials have wide sources, meanwhile, the vegetable oil polyol A2 has excellent cohesiveness, low temperature resistance and water resistance, the isocyanate A3 and the isocyanate A4 can be obtained from commercial channels, wherein the isocyanate A3 can be TDI, IPDI, PAPI, MDI and NDI, and 2-functionality liquid isocyanate is generally preferred; isocyanate a4 modified isocyanate modified by carbodiimide or uretonimine; polyether polyol B1 and polyol B2 are polymer polyols with EO or PO as polymerization monomers, wherein polyol B2 is a modified polymer polyol containing a small amount of-SH groups or-NH 2 groups, and polyether polyol B1 can also be vegetable oil polyol A2; the molecular weights of polymer polyol B1 and polyol B2 are selected to be 300-3000, and most preferably 350-1500; chain extender B3 is low molecular weight dihydric alcohol/amine, trihydric alcohol/amine and micromolecular polyhydric alcohol with tetrafunctionality higher than tetrafunctional degree, such as pentaerythritol, sucrose alcohol, maltitol, etc., preferably dihydric alcohol/amine and trihydric alcohol/amine, such as ethylene glycol, ethylenediamine, glycerol and triethanolamine; the leveling assistant B4 is mainly acrylate high molecular polymer or organosilicon high molecular polymer used alone or in combination; the proportion of the polymer polyol in the main agent before reaction is 30-60%, and the most preferable proportion is 35-45%; isocyanate A3 in a ratio of 30 to 50%, most preferably 35 to 45%; 5-25% of isocyanate A4, most preferably 12-20%; the polymer is blocked by isocyanate groups, so that no hydroxyl group exists, and the storage stability of the product is ensured.
Because the polyurethane has side reactions during the curing reaction, such as polyurea and carbon dioxide produced by the reaction with moisture, and allophanate and carbon dioxide produced by the further crosslinking and curing of carbamate and isocyanate, it is preferable that the number of the reaction groups of the main agent and the curing agent is as close as possible in the formulation design process, so as to avoid excessive side reactions, and further ensure no "waste gas" in the double-barrier structure, thereby ensuring the product appearance and reliable adhesion, therefore, in the formulation design of the main agent and the curing agent, the ratio R of the number of the isocyanate groups to the number of the active reaction groups must be 1.01-1.65, most preferably 1.3-1.4, if less than 1.01, the curing agent is too little, the complete curing cannot be performed, or the tray storage time in the construction process is too short, the construction cannot be performed, if more than 1.65, the side reactions are likely to occur, resulting in poor appearance of the finished product.
In the preparation process of the finished product, a lower preparation temperature is selected, so that the reaction can be fully completed, and the phenomenon of yellowing of the appearance of the finished product is remarkably reduced, because double bonds in isocyanate A3 and isocyanate A4 are oxidized, and particularly, the isocyanate with a benzene ring structure is easy to yellow at a high temperature; uniformly mixing the prepared main agent and the curing agent at 35-45 ℃ by a static mixing pipe according to the mass ratio of 100:60-70, compounding the film material on a solvent-free coating machine, suspending the compounded laminated film in a drying room at 40-45 ℃ for curing for 7-12 hours, preferably 8-10 hours, and then sampling for detection and analysis.
Comparative example 1:
the preparation method of the main agent comprises the following steps: a. 124.2 parts of polyether polyol A with the molecular weight of 2000, 28.5 parts of vegetable oil polyol A with the molecular weight of 1000, 1.9 parts of polyol with the molecular weight of 400 and 13 parts of polyether polyol A with the molecular weight of 350 are added into a three-port reaction kettle; b. heating and heating, stirring, adding MDI-5060 parts when the temperature reaches 50 ℃, and then reacting for 2 hours at the constant temperature of 60 ℃; c. 2.4 parts of MDI-100LL is added, and the reaction is continued for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. taking another clean three-neck flask, and adding 130 parts of polyether polyol B with molecular weight of 2000, 115 parts of polyether polyol B with molecular weight of 1000, 113 parts of polyether polyol B with molecular weight of 500, 5 parts of chain extender B3 diethylene glycol and 237 parts of vegetable oil polyol A; b. mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 90min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
Comparative example 2:
the preparation method of the main agent comprises the following steps: a. 190 parts of polyether polyol A with the molecular weight of 2000 and 118 parts of polyether polyol A with the molecular weight of 400 are added into a three-port reaction kettle; b. heating and heating, stirring, adding MDI-5098 parts when the temperature reaches 50 ℃, and then reacting for 2 hours at constant temperature of 60 ℃; c. adding 28 parts of MDI-100LL, and continuously reacting for 1 hour at the constant temperature of 60 ℃; d. vacuum defoaming for 30min under-0.1 MPa; e. filtering and discharging to obtain the main agent.
The preparation method of the curing agent comprises the following steps: a. adding 280 parts of vegetable oil polyol A with the molecular weight of 1000, 110 parts of polyether polyol B with the molecular weight of 500 and 10 parts of chain extender B3 diethylene glycol into another clean three-neck flask; b. mixing, stirring and heating to 50 ℃; c. vacuum defoaming for 90min under-0.1 MPa; d. filtering and discharging to obtain the curing agent.
The adhesive prepared in the above examples and comparative examples was subjected to film/film lamination and aging at 40 ℃, and then subjected to appearance and peel strength tests according to GB/T10004-2008, with the results as follows:
from the above table, the hardness of the glue layer is not much different between the examples and the comparison examples, which are soft, and the comparison examples are compared with the material application requirements in the field of composite flexible packaging, and the comparison examples can not meet the application requirements judged from the appearance of the finished product, and in addition, the comparison examples can not meet the requirements according to the strength detection requirements in the plastic and aluminum foil composite film for food packaging and the bag standard GB/T28118-. The two-component solvent-free polyurethane adhesive developed by the patent not only meets the detection standard, but also is better.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The adhesive for flexible package compounding is characterized by comprising a main agent blocked by isocyanate groups and a curing agent blocked by hydroxyl groups, wherein the main agent mainly comprises the following components: polyether polyol A1, vegetable oil polyol A2, isocyanate A3 and isocyanate A4, wherein the curing agent mainly comprises the following components: polyether polyol B1, polyol B2, chain extender B3 and leveling aid B4.
2. The adhesive for compounding flexible packages of claim 1, wherein the polyether polyol A1 is mainly a di-functional polyol and a tri-functional polyol using PO as a polymerization monomer, and has a molecular weight of 300-.
3. The adhesive for compounding flexible packages according to claim 2, wherein the vegetable oil polyol a2 is specifically any one of soybean oil polyol, palm oil polyol and castor oil polyol.
4. The adhesive for flexible packaging composite according to claim 3, wherein the isocyanate A3 is one of TDI, IPDI, PAPI, MDI and NDI, and the isocyanate A4 is modified isocyanate modified by carbodiimide or uretonimine.
5. The adhesive for compounding flexible packages according to claim 2, wherein the chain extender B3 is any one of low molecular weight diols/amines, triols/amines, pentaerythritol, sucrose alcohols and maltitol.
6. The adhesive for flexible package composition of claim 5, wherein the leveling agent B4 is one or two of acrylate polymer and silicone polymer.
7. The adhesive for compounding flexible packages of claim 1, wherein the adhesive enables direct compound lamination of two or more layers of high barrier material.
8. A method for preparing an adhesive for flexible packaging compositions comprising an adhesive for flexible packaging compositions according to any one of claims 1 to 7, characterized in that it comprises the following steps:
s1, preparing a main agent;
s2, preparing a curing agent;
s3, uniformly mixing the prepared main agent and the curing agent through a static mixing pipe at the temperature of 35-45 ℃ according to the mass ratio of 100: 60-70;
s4, compounding the membrane material on a solvent-free coating machine;
s5, the compounded laminated film is suspended in a drying room at 40-45 ℃ to be cured for 7-12 hours, and then sampling is carried out for detection and analysis.
9. The method of preparing an adhesive for compounding flexible packages according to claim 8, wherein the step of preparing a base in step S1 comprises:
a. adding any one or a mixture of polyether polyol A1 and vegetable oil polyol A2 with the water content of less than 0.05 percent into a three-port reaction kettle;
b. stirring and heating to 50 ℃, adding isocyanate A3, and then reacting for several hours at constant temperature of 55-65 ℃;
c. adding isocyanate A4, and continuing to react at constant temperature;
d. placing under-0.1 MPa for vacuum defoaming for 30-45 min;
e. filtering and discharging to obtain the main agent.
10. The method for preparing an adhesive for compounding flexible packages according to claim 8, wherein the step of preparing the curing agent in step S2 is:
a. adding polyether polyol B1, polyol B2, a chain extender B3 and a leveling assistant B4 into a three-port reaction kettle;
b. mixing, stirring and heating to 40-60 ℃;
c. placing under-0.1 MPa for vacuum defoaming for 60-90 min;
d. filtering and discharging to obtain the curing agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111999A (en) * | 2015-09-18 | 2015-12-02 | 北京高盟新材料股份有限公司 | Binding agent for solvent-free two-component polyurethane composite film, and preparation method for binding agent |
| CN107118734A (en) * | 2017-06-02 | 2017-09-01 | 新纶复合材料科技（常州）有限公司 | A kind of double component solvent-free polyurethane adhesive |
| CN110128612A (en) * | 2019-06-04 | 2019-08-16 | 无锡市万力粘合材料股份有限公司 | The preparation method of food flexible packing high temperature resistant type complex function adhesive |
| CN110684502A (en) * | 2019-11-13 | 2020-01-14 | 江苏华大新材料有限公司 | Solvent-free two-component polyurethane adhesive for aluminum plating transfer resistance and preparation method thereof |
-
2020
- 2020-09-24 CN CN202011018246.3A patent/CN112094618A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111999A (en) * | 2015-09-18 | 2015-12-02 | 北京高盟新材料股份有限公司 | Binding agent for solvent-free two-component polyurethane composite film, and preparation method for binding agent |
| CN107118734A (en) * | 2017-06-02 | 2017-09-01 | 新纶复合材料科技（常州）有限公司 | A kind of double component solvent-free polyurethane adhesive |
| CN110128612A (en) * | 2019-06-04 | 2019-08-16 | 无锡市万力粘合材料股份有限公司 | The preparation method of food flexible packing high temperature resistant type complex function adhesive |
| CN110684502A (en) * | 2019-11-13 | 2020-01-14 | 江苏华大新材料有限公司 | Solvent-free two-component polyurethane adhesive for aluminum plating transfer resistance and preparation method thereof |
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Application publication date: 20201218 |