CN115044020B - Application of polyester polyol in adhesive for food packaging - Google Patents

Application of polyester polyol in adhesive for food packaging Download PDF

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Publication number
CN115044020B
CN115044020B CN202111238513.2A CN202111238513A CN115044020B CN 115044020 B CN115044020 B CN 115044020B CN 202111238513 A CN202111238513 A CN 202111238513A CN 115044020 B CN115044020 B CN 115044020B
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polyester polyol
adhesive
dibasic acid
dihydric alcohol
food packaging
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CN115044020A (en
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蔡建国
龙双林
张曦
徐震华
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Shanghai Lejoin High Molecular Material Co ltd
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Shanghai Lejoin High Molecular Material Co ltd
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C09J175/06—Polyurethanes from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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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 relates to the field of IPC C08G63/00, in particular to application of polyester polyol in an adhesive for food packaging. The polyester polyol accounts for 40-68wt% of the total weight of the raw materials of the adhesive for food packaging. Has the following advantages: adopting the combined action of specific acid and alcohol to obtain polyester polyol with low water content and controllable hydroxyl value; the polyester polyol with a specific molecular structure is applied to the adhesive, and the obtained adhesive product has excellent bonding strength and can be applied to sealing of various food packaging materials (such as PE, PET, AL, CPP and the like); the adhesive is prepared by compounding aromatic isocyanate and aliphatic isocyanate and reacting with specific polyester polyol, has extremely strong steaming resistance, and is easy to yellow and fall off in food medium, and the like, and the weather resistance and the lasting effect of the adhesive are improved.

Description

Application of polyester polyol in adhesive for food packaging
Technical Field
The invention relates to the field of IPC C08G63/00, in particular to application of polyester polyol in an adhesive for food packaging.
Background
With the improvement of the quality of life and the consumption level of people, safe and environment-friendly food packages are more and more favored by people. Polyurethane adhesive is used as a chemical with controllable structure and diversified properties, and is a popular choice for bonding materials for food packaging. However, the food package has high requirements on the adhesive, and the common adhesive is difficult to meet the use requirement because the adhesive is in contact with food for a long time and needs to be matched with the processing operation of the food during the sealing process.
Chinese patent CN201810389675.8 discloses a preparation method of a waterproof environment-friendly polyurethane adhesive, which adopts xanthan gum, carbodiimide, glutamic acid to react with xylylene diisocyanate, polycaprolactone diol and the like to obtain environment-friendly waterproof polyurethane, but the polyurethane adhesive provided by the prior art is mainly applied to the building industry and cannot be effectively applied to the adhesion of food flexible packaging materials. Chinese patent CN201310448049.9 discloses a method for synthesizing aqueous polyurethane adhesive for compounding PVDC film and other flexible packaging film, which comprises reacting polyether polyol and polyester polyol with toluene diisocyanate to obtain packaging material with good barrier property. However, the application range of the adhesive is limited, and the adhesive can not meet the bonding of various food packaging materials.
Under such a background, the investigation of a food packaging adhesive with strong adhesiveness and safety and stability is a problem to be solved in the art.
Disclosure of Invention
The invention provides the application of the polyester polyol in the adhesive for food packaging, solves the defects of easy failure and poor steaming resistance of the adhesive for food packaging in the prior art, and realizes the adhesive for food packaging, which has strong cohesiveness, safety and stability.
In a first aspect, the invention provides the use of a polyester polyol in an adhesive for food packaging, the polyester polyol comprising 40 to 68wt% of the total weight of the raw materials of the adhesive for food packaging.
In order to improve the bonding strength of the adhesive to the food packaging substrate, in some preferred embodiments, the polyester polyol has a hydroxyl value of 25 to 70mgKOH/g, a solids content of 60 to 75wt% and a moisture content of 300ppm or less. The invention discovers that the polyester polyol meeting the conditions can react and crosslink with isocyanate, chain extender and the like to form a segmented copolymer with rich polar bonds, endows the adhesive layer with stronger bonding strength, obviously improves the steaming resistance of the adhesive layer, improves the dielectric resistance of the adhesive for food packaging and has lasting effect.
In some preferred embodiments, the polyester polyol comprises a starting material comprising a diacid and a diol in a weight ratio of (5-7): (2-6).
In some preferred embodiments, the diacid comprises an aromatic diacid and/or an aliphatic diacid.
In some preferred embodiments, the diacid includes at least aromatic diacid where the carbon atoms to which 2 carboxyl groups are attached are in an ortho, meta, or para position distribution.
In some preferred embodiments, the dibasic acid comprises at least an aliphatic dibasic acid comprising a linear aliphatic dibasic acid having a melting point of 102-184 ℃.
In some preferred embodiments, the aliphatic dibasic acid has a flash point of 150 to 240 ℃.
Examples of aliphatic dibasic acids having a melting point of 102-184 ℃ and a flash point of 150-240 ℃ include, but are not limited to, adipic acid, sebacic acid, azelaic acid.
The adipic acid has a melting point of 152 ℃ and a flash point of 196 ℃. The sebacic acid has a melting point of 134 ℃ and a flash point of 220 ℃. The melting point of azelaic acid was 107 ℃ and the flash point was 210 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, wherein the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is (0.2-3): (1-4).
The linear dihydric alcohol comprises one or more of 1, 4-butanediol, ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 6-hexanediol and 1, 7-heptanediol.
The branched diol comprises one or more of neopentyl glycol, methyl propylene glycol, 3-methyl-1, 5-pentanediol, dipropylene glycol, 2, 4-diethyl-1, 5-pentanediol, and 2, 4-trimethyl-1, 3-pentanediol.
Through a great deal of experimental researches, the invention discovers that the polyester polyol is subjected to specific molecular structure design, and the heat resistance and the water vapor permeability of the adhesive can be obviously improved by adopting the combined action of the aromatic dibasic acid and the aliphatic dibasic acid and the linear dibasic alcohol and the branched chain dibasic alcohol; particularly, the aromatic dibasic acid and the branched chain dihydric alcohol are adopted to carry out esterification reaction, then the aliphatic dibasic acid and the linear dihydric alcohol are added to carry out reaction, and finally the obtained adhesive material generated by the polyester polyol reaction has the performances of heat resistance, high temperature resistance, solvent resistance and the like, and can effectively seal food packaging (especially flexible packaging), thereby solving the technical problems that the adhesive layer is easy to fall off, crack and corrode when the food packaging is carried out, has poor weather resistance and is easy to lose efficacy along with the food processing process.
In some preferred embodiments, the polyester polyol is prepared by the steps of: and sequentially mixing and reacting the aromatic dibasic acid, the branched chain dihydric alcohol, the aliphatic dibasic acid and the linear dihydric alcohol to obtain a polyester polyol finished product.
Further preferably, the polyester polyol is prepared by the steps of: adding aromatic dibasic acid and branched chain dihydric alcohol into a reaction kettle, reacting at 175-190 ℃ until the acid value is 15-25mgKOH/g, cooling to 50-100 ℃, sequentially adding aliphatic dibasic acid and linear dihydric alcohol, heating to 140-155 ℃, and reacting until the viscosity (75 ℃) is 7000-13000 mPa.s, thus obtaining the polyester polyol product.
In some preferred embodiments, the polyester polyol can be directly subjected to subsequent reaction, can be diluted and reduced in viscosity, and can be used according to actual conditions, so that great convenience is provided for the synthesis and application of the adhesive in operation.
In some preferred embodiments, the raw materials of the adhesive for food packaging comprise, by weight, 36-54 parts of polyester polyol, 20-30 parts of diisocyanate, 1-8 parts of chain extender and 2-12 parts of solvent.
The diisocyanate is a diisocyanate commonly used in the art, such as TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), HDI (1, 6-hexamethylene diisocyanate).
Traditional adhesives generally adopt TDI with higher activity, but the TDI has higher risk and is not suitable for being used in adhesives for food packaging. In order to achieve both curing speed and adhesive strength, it is preferred that the diisocyanate is MDI and HDI, the weight ratio of MDI and HDI being (1.5-4): 1. the invention discovers that the MDI is matched with a small amount of aliphatic isocyanate to act together, and the polyester polyol with a specific molecular structure is matched, so that the problem that the curing speed, weather resistance and yellowing resistance of the existing polyurethane adhesive can not be considered can be solved, and the obtained adhesive has the advantages of high curing speed, strong weather resistance, difficult yellowing and the like, can meet the bonding of a plurality of types of materials such as PE, PET, AL, CPP and the like, and ensures that the food package maintains a long-term sealing effect.
In some preferred embodiments, the chain extender is a polyol and/or polyamine.
In some preferred embodiments, the catalyst is an amine catalyst and/or an organometallic catalyst, the amine catalyst including, but not limited to, dimethylcyclohexylamine, bis (2-methylaminoethyl) ether, or 1,3, 5-tris (dimethylaminopropyl) hexaaminotriazine, dimethylbenzylamine, triethylenediamine; the organometallic catalyst includes, but is not limited to, one or more of potassium salts of unsaturated acids, zinc acetate, dibutyltin dilaurate or stannous octoate.
In some preferred embodiments, the method for preparing the adhesive for food packaging comprises the following steps:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 70-85 ℃ for 1-3 hours to obtain a prepolymer A;
s3, adding a chain extender and a solvent into the prepolymer A, and carrying out heat preservation reaction for 2-6 hours to obtain a prepolymer B;
s4, adding deionized water into the prepolymer B for dispersion and emulsification, and vacuumizing to remove the solvent to obtain a finished product of the adhesive for food packaging.
The beneficial effects are that:
the invention provides an application of polyester polyol in an adhesive for food packaging, which has the following advantages:
(1) The polyester polyol with low water content and controllable hydroxyl value is obtained by adopting the combined action of specific aromatic dibasic acid, branched chain dihydric alcohol, aliphatic dibasic acid and linear dihydric alcohol;
(2) The polyester polyol with a specific molecular structure is applied to the adhesive, and the obtained adhesive product has excellent bonding strength and can be applied to sealing of various food packaging materials (such as PE, PET, AL, CPP and the like);
(3) The adhesive is prepared by compounding aromatic isocyanate and aliphatic isocyanate and reacting with specific polyester polyol, has extremely strong steaming resistance, and is easy to yellow and fall off in food medium, and the like, and the weather resistance and the lasting effect of the adhesive are improved.
Detailed Description
Example 1.
The embodiment provides application of polyester polyol in an adhesive for food packaging.
The raw materials of the polyester polyol comprise dibasic acid and dihydric alcohol, wherein the weight ratio of the dibasic acid to the dihydric alcohol is 6:4.4.
the dibasic acid comprises aromatic dibasic acid and aliphatic dibasic acid; the weight ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1:1.
The aromatic dibasic acid is refined terephthalic acid and is derived from Yangzi petrochemical industry.
The aliphatic dibasic acid is adipic acid; adipic acid has a melting point of 152℃and a flash point of 196 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, wherein the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is 1.8:2.6.
the linear dihydric alcohol is 1, 4-butanediol.
The branched diol is neopentyl glycol and methyl propylene glycol, and the molar ratio of the neopentyl glycol to the methyl propylene glycol is 8:1.
The preparation steps of the polyester polyol are as follows: adding aromatic dibasic acid and branched diol into a reaction kettle, reacting at 185 ℃ until the acid value is 20mgKOH/g, cooling to 80 ℃, sequentially adding aliphatic dibasic acid and linear diol, heating to 150 ℃, and reacting until the viscosity (75 ℃) is 10000+/-500 mPa.s, thus obtaining the polyester polyol product.
The raw materials of the adhesive for food packaging comprise 48 parts by weight of polyester polyol, 27 parts by weight of diisocyanate, 3 parts by weight of chain extender, 0.1 part by weight of catalyst and 6 parts by weight of solvent.
The diisocyanate is MDI and HDI, and the weight ratio of the MDI to the HDI is 3:1.
the chain extender is trimethylolpropane and ethylene glycol, and the weight ratio of the trimethylolpropane to the ethylene glycol is 1:1.
The catalyst is dibutyl tin dilaurate.
The solvent is acetone.
The preparation method of the adhesive for food packaging comprises the following steps:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 80 ℃ for 1.5 hours to obtain a prepolymer A;
s3, cooling to 50 ℃, adding a chain extender, a catalyst and a solvent into the prepolymer A, and carrying out heat preservation reaction for 3 hours to obtain a prepolymer B;
s4, adding deionized water (the addition amount of the deionized water is 2 times of the mass of the polyester polyol) into the prepolymer B for dispersing and emulsifying, and vacuumizing to remove the solvent to obtain a finished product of the adhesive for food packaging.
Example 2.
The embodiment provides application of polyester polyol in an adhesive for food packaging.
The raw materials of the polyester polyol comprise dibasic acid and dihydric alcohol, wherein the weight ratio of the dibasic acid to the dihydric alcohol is 6:3.5.
the dibasic acid comprises aromatic dibasic acid and aliphatic dibasic acid; the weight ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1:1.
The aromatic dibasic acid is refined terephthalic acid and is derived from Yangzi petrochemical industry.
The aliphatic dibasic acid is adipic acid; adipic acid has a melting point of 152℃and a flash point of 196 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, wherein the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is 1.5:2.
the linear dihydric alcohol is 1, 4-butanediol.
The branched diol is neopentyl glycol and methyl propylene glycol, and the molar ratio of the neopentyl glycol to the methyl propylene glycol is 8:1.
The preparation steps of the polyester polyol are as follows: adding aromatic dibasic acid and branched diol into a reaction kettle, reacting at 185 ℃ until the acid value is 20mgKOH/g, cooling to 80 ℃, sequentially adding aliphatic dibasic acid and linear diol, heating to 150 ℃, and reacting until the viscosity (75 ℃) is 10000+/-500 mPa.s, thus obtaining the polyester polyol product.
The raw materials of the adhesive for food packaging comprise 48 parts by weight of polyester polyol, 27 parts by weight of diisocyanate, 3 parts by weight of chain extender, 0.1 part by weight of catalyst and 6 parts by weight of solvent.
The diisocyanate is MDI and HDI, and the weight ratio of the MDI to the HDI is 3:1.
the chain extender is trimethylolpropane and ethylene glycol, and the weight ratio of the trimethylolpropane to the ethylene glycol is 1:1.
The catalyst is dibutyl tin dilaurate.
The solvent is acetone.
The preparation method of the adhesive for food packaging comprises the following steps:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 80 ℃ for 1.5 hours to obtain a prepolymer A;
s3, cooling to 50 ℃, adding a chain extender, a catalyst and a solvent into the prepolymer A, and carrying out heat preservation reaction for 3 hours to obtain a prepolymer B;
s4, adding deionized water (the addition amount of the deionized water is 2 times of the mass of the polyester polyol) into the prepolymer B for dispersing and emulsifying, and vacuumizing to remove the solvent to obtain a finished product of the adhesive for food packaging.
Example 3.
The embodiment provides application of polyester polyol in an adhesive for food packaging.
The raw materials of the polyester polyol comprise dibasic acid and dihydric alcohol, wherein the weight ratio of the dibasic acid to the dihydric alcohol is 6:4.4.
the dibasic acid comprises aromatic dibasic acid and aliphatic dibasic acid; the weight ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1:1.
The aromatic dibasic acid is refined terephthalic acid and is derived from Yangzi petrochemical industry.
The aliphatic dibasic acid is adipic acid; adipic acid has a melting point of 152℃and a flash point of 196 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, wherein the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is 1.8:2.6.
the linear dihydric alcohol is 1, 4-butanediol.
The branched diol is 3-methyl-1, 5-pentanediol.
The preparation steps of the polyester polyol are as follows: adding aromatic dibasic acid and branched diol into a reaction kettle, reacting at 185 ℃ until the acid value is 20mgKOH/g, cooling to 80 ℃, sequentially adding aliphatic dibasic acid and linear diol, heating to 150 ℃, and reacting until the viscosity (75 ℃) is 10000+/-500 mPa.s, thus obtaining the polyester polyol product.
The raw materials of the adhesive for food packaging comprise 48 parts by weight of polyester polyol, 27 parts by weight of diisocyanate, 3 parts by weight of chain extender, 0.1 part by weight of catalyst and 6 parts by weight of solvent.
The diisocyanate is MDI and HDI, and the weight ratio of the MDI to the HDI is 3:1.
the chain extender is trimethylolpropane and ethylene glycol, and the weight ratio of the trimethylolpropane to the ethylene glycol is 1:1.
The catalyst is dibutyl tin dilaurate.
The solvent is acetone.
The preparation method of the adhesive for food packaging comprises the following steps:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 80 ℃ for 1.5 hours to obtain a prepolymer A;
s3, cooling to 50 ℃, adding a chain extender, a catalyst and a solvent into the prepolymer A, and carrying out heat preservation reaction for 3 hours to obtain a prepolymer B;
s4, adding deionized water (the addition amount of the deionized water is 2 times of the mass of the polyester polyol) into the prepolymer B for dispersing and emulsifying, and vacuumizing to remove the solvent to obtain a finished product of the adhesive for food packaging.
Comparative example 1.
This comparative example provides the use of a polyester polyol in an adhesive for food packaging, the embodiment being the same as example 1; the difference is that the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is 2:1.
comparative example 2.
This comparative example provides the use of a polyester polyol in an adhesive for food packaging, the embodiment being the same as example 1; the difference is that the diisocyanate is MDI and HDI, and the weight ratio of the MDI to the HDI is 1:1.
performance test method
1. Physical and chemical index of polyester polyol
The physical and chemical indexes of the polyester polyols obtained in examples 1 to 3 and comparative example 1 are shown in Table 1.
Wherein the determination of the hydroxyl number is referred to ASTM D4274; moisture determination refers to ASTM D4672.
2. Adhesive properties
(1) Adhesion: PP (polypropylene) films were compounded with the adhesives obtained in examples 1 to 3 and comparative examples 1 to 2, cured at 50℃for 20 hours, cut into 200mm X30 mm specimens, and tested for T-type peel strength of 100mm/min with reference to GB/T2791-1995; the results are shown in Table 2.
(2) Retort resistance: the test pieces obtained in examples 1 to 3 and comparative examples 1 to 2 were allowed to stand at 121℃for 40 minutes, and the decrease rate δ of T-type peel strength was calculated; defining delta less than or equal to 10 percent as qualified and delta more than 10 percent as unqualified; the results are shown in Table 2.
Performance test data
Table 1.
TABLE 2

Claims (1)

1. The application of the polyester polyol in the adhesive for food packaging is characterized in that the raw materials of the polyester polyol comprise dibasic acid and dihydric alcohol, and the weight ratio of the dibasic acid to the dihydric alcohol is 6:4.4;
the dibasic acid comprises aromatic dibasic acid and aliphatic dibasic acid; the weight ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1:1;
the aromatic dibasic acid is refined terephthalic acid;
the aliphatic dibasic acid is adipic acid; adipic acid has a melting point of 152 ℃ and a flash point of 196 ℃;
the dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, wherein the weight ratio of the linear dihydric alcohol to the branched dihydric alcohol is 1.8:2.6;
the linear dihydric alcohol is 1, 4-butanediol;
the branched diol is neopentyl glycol and methyl propylene glycol, and the molar ratio of the neopentyl glycol to the methyl propylene glycol is 8:1;
the preparation steps of the polyester polyol are as follows: adding aromatic dibasic acid and branched chain dihydric alcohol into a reaction kettle, reacting at 185 ℃ until the acid value is 20mgKOH/g, cooling to 80 ℃, sequentially adding aliphatic dibasic acid and linear dihydric alcohol, heating to 150 ℃, and measuring 10000+/-500 mPa.s when the viscosity is 75 ℃ to obtain a polyester polyol product;
the raw materials of the adhesive for food packaging comprise 48 parts by weight of polyester polyol, 27 parts by weight of diisocyanate, 3 parts by weight of chain extender, 0.1 part by weight of catalyst and 6 parts by weight of solvent;
the diisocyanate is MDI and HDI, and the weight ratio of the MDI to the HDI is 3:1, a step of;
the chain extender is trimethylolpropane and ethylene glycol, and the weight ratio of the trimethylolpropane to the ethylene glycol is 1:1;
the catalyst is dibutyl tin dilaurate;
the solvent is acetone;
the preparation method of the adhesive for food packaging comprises the following steps:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 80 ℃ for 1.5 hours to obtain a prepolymer A;
s3, cooling to 50 ℃, adding a chain extender, a catalyst and a solvent into the prepolymer A, and carrying out heat preservation reaction for 3 hours to obtain a prepolymer B;
s4, adding deionized water into the prepolymer B, wherein the adding amount of the deionized water is 2 times of the mass of the polyester polyol, dispersing and emulsifying, and vacuumizing to remove the solvent to obtain a finished product of the adhesive for food packaging.
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