CN115044020A - Application of polyester polyol in adhesive for food packaging - Google Patents

Application of polyester polyol in adhesive for food packaging Download PDF

Info

Publication number
CN115044020A
CN115044020A CN202111238513.2A CN202111238513A CN115044020A CN 115044020 A CN115044020 A CN 115044020A CN 202111238513 A CN202111238513 A CN 202111238513A CN 115044020 A CN115044020 A CN 115044020A
Authority
CN
China
Prior art keywords
polyester polyol
adhesive
food packaging
dibasic acid
dihydric alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111238513.2A
Other languages
Chinese (zh)
Other versions
CN115044020B (en
Inventor
蔡建国
龙双林
张曦
徐震华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Lejoin High Molecular Material Co ltd
Original Assignee
Shanghai Lejoin High Molecular Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Lejoin High Molecular Material Co ltd filed Critical Shanghai Lejoin High Molecular Material Co ltd
Priority to CN202111238513.2A priority Critical patent/CN115044020B/en
Publication of CN115044020A publication Critical patent/CN115044020A/en
Application granted granted Critical
Publication of CN115044020B publication Critical patent/CN115044020B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Abstract

The invention relates to the field of IPC 08G63/00, in particular to application of polyester polyol in an adhesive for food packaging. The polyester polyol accounts for 40-68 wt% of the total weight of the raw materials of the adhesive for food packaging. Has the following advantages: obtaining polyester polyol with low water content and controllable hydroxyl value by adopting the combined action of specific acid and alcohol; 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 aromatic isocyanate and the aliphatic isocyanate are compounded and react with the specific polyester polyol, so that the obtained adhesive has extremely strong boiling resistance, the adhesive is effectively inhibited from being easily yellowed, easily dropped and the like in a food medium, 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 08G63/00, in particular to application of polyester polyol in an adhesive for food packaging.
Background
Along with the improvement of the living quality and the consumption level of people, safe and environment-friendly food packages are more and more favored by people. Polyurethane adhesives are used as a chemical with controllable structure and diversified performance, and become the popular choice for bonding materials for food packaging. However, the requirement of food packaging on the adhesive is high, and the common adhesive is often difficult to meet the use requirement due to the fact that 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 method for preparing a waterproof environment-friendly polyurethane adhesive, which adopts xanthan gum, carbodiimide, glutamic acid to react with xylylene diisocyanate, polycaprolactone diol, etc. 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 waterborne polyurethane adhesive for compounding PVDC films and other flexible packaging films, which comprises the step of reacting polyether polyol and polyester polyol with toluene diisocyanate to obtain a packaging material with good barrier property. However, the application range of the adhesive is limited, and the adhesive cannot meet the bonding of various food packaging materials.
Under such circumstances, it is an urgent need in the art to find a safe and stable adhesive for food packaging having high adhesiveness.
Disclosure of Invention
The invention provides the application of the polyester polyol in the adhesive for food packaging, overcomes the defects that the adhesive for food packaging in the prior art is easy to lose efficacy and has poor steaming resistance, and realizes the adhesive for food packaging which has strong adhesion, safety and stability.
The invention provides in a first aspect the use of a polyester polyol in an adhesive for food packaging, the polyester polyol comprising from 40 to 68% by weight of the total weight of the starting materials for the food packaging adhesive.
In order to improve the bonding strength of the adhesive and the food packaging substrate, in some preferred embodiments, the hydroxyl value of the polyester polyol is 25-70mgKOH/g, the solid content is 60-75 wt%, and the moisture is less than or equal to 300 ppm. The invention discovers that the polyester polyol meeting the conditions can react with isocyanate, a chain extender and the like for crosslinking to form a block copolymer with rich polar bonds, so that the adhesive layer is endowed with stronger bonding strength, the boiling resistance of the adhesive layer is obviously improved, the medium resistance of the adhesive for food packaging is improved, and the effect is lasting.
In some preferred embodiments, 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 (5-7): (2-6).
In some preferred embodiments, the dibasic acid comprises an aromatic dibasic acid and/or an aliphatic dibasic acid.
In some preferred embodiments, the diacid includes at least an aromatic diacid in which the carbon atoms to which the 2 carboxyl groups are attached are distributed ortho, meta, or para.
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 150-240 ℃.
Examples of aliphatic dibasic acids having melting points of 102-184 ℃ and flash points of 150-240 ℃ include, but are not limited to, adipic acid, sebacic acid, and azelaic acid.
The adipic acid had a melting point of 152 ℃ and a flash point of 196 ℃. The melting point of the sebacic acid is 134 ℃ and the flash point is 220 ℃. The melting point of azelaic acid is 107 ℃ and the flash point is 210 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched dihydric alcohol, and 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 2,2, 4-trimethyl-1, 3-pentanediol.
According to the invention, through a large amount of experimental researches, the specific molecular structure design of the polyester polyol is found, and the heat resistance and the water vapor permeability resistance of the adhesive can be remarkably improved by adopting the combined action of aromatic dibasic acid, aliphatic dibasic acid, linear dihydric alcohol and branched dihydric alcohol; particularly, aromatic dibasic acid and branched chain dihydric alcohol are firstly subjected to esterification reaction, then aliphatic dibasic acid and linear dihydric alcohol are added for reaction, finally the obtained polyester polyol is subjected to reaction to generate a glue material which has the properties of humidity resistance, heat resistance, high temperature resistance, solvent resistance and the like, the adhesive can be used for effectively sealing food packages (particularly flexible packages), and the technical problems that the glue layer is easy to fall off, crack and corrode, the weather resistance is poor and the glue layer is easy to lose efficacy along with the food processing process during food packaging are solved.
In some preferred embodiments, the polyester polyol is prepared by the steps of: and mixing and reacting the aromatic dibasic acid, the branched chain dihydric alcohol, the aliphatic dibasic acid and the linear dihydric alcohol in sequence to obtain a polyester polyol finished product.
Further preferably, 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 the temperature of 175-190 ℃ until the acid value is 15-25mgKOH/g, cooling to the temperature of 50-100 ℃, sequentially adding aliphatic dibasic acid and linear dihydric alcohol, heating to the temperature of 140-155 ℃, and reacting until the viscosity (75 ℃) is 7000-13000 mPa.s to obtain a polyester polyol product.
In some preferred embodiments, the polyester polyol can be directly subjected to subsequent reaction, or can be diluted to reduce viscosity and then be used according to actual conditions, so that great convenience is brought to 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 diisocyanates are the diisocyanates customary in the art, such as TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), HDI (1, 6-hexamethylene diisocyanate).
The conventional adhesive usually adopts TDI with higher activity, but the TDI has higher risk and is not suitable for being used in the adhesive for food packaging. In order to achieve both of curing speed and adhesive strength, preferably, the diisocyanate is MDI and HDI, and the weight ratio of MDI to HDI is (1.5 to 4): 1. the invention discovers that the problem that the curing speed, weather resistance and yellowing resistance of the existing polyurethane adhesive can not be simultaneously considered by adopting the combined action of MDI and a small amount of aliphatic isocyanate and matching with polyester polyol with a specific molecular structure 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 various materials such as PE, PET, AL, CPP and the like, and can keep the long-term sealing effect of food packages.
In some preferred embodiments, the chain extender is a polyol and/or polyamine compound.
In some preferred embodiments, the catalyst is an amine catalyst including, but not limited to, dimethylcyclohexylamine, bis (2-methylaminoethyl) ether or 1,3, 5-tris (dimethylaminopropyl) hexa-aminotriazine, dimethylbenzylamine, triethylenediamine; organometallic catalysts include, but are not limited to, one or more of the unsaturated acid potassium salts, zinc acetate, dibutyltin dilaurate, or stannous octoate.
In some preferred embodiments, the method of preparing the adhesive for food packaging comprises:
s1, preparing polyester polyol;
s2, reacting polyester polyol with diisocyanate at 70-85 ℃ for 1-3h 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;
and S4, adding deionized water 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.
Has the advantages that:
the invention provides an application of polyester polyol in an adhesive for food packaging, which has the following advantages:
(1) specific aromatic dibasic acid, branched chain dihydric alcohol, aliphatic dibasic acid and linear dihydric alcohol are adopted to act together to obtain polyester polyol with low water content and controllable hydroxyl value;
(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) aromatic isocyanate and aliphatic isocyanate are compounded and react with specific polyester polyol, so that the obtained adhesive has extremely strong boiling resistance, the adhesive is easy to yellow and fall off in food media, and the weather resistance and the lasting effect of the adhesive are improved.
Detailed Description
Example 1.
This example provides the use of a polyester polyol in an adhesive for food packaging.
The polyester polyol comprises the following raw materials in parts by weight: 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 purified terephthalic acid and is derived from the petrifaction of a raisin.
The aliphatic dibasic acid is adipic acid; the melting point of adipic acid was 152 ℃ and the flash point was 196 ℃.
The dihydric alcohol comprises linear dihydric alcohol and branched chain dihydric alcohol, and the weight ratio of the linear dihydric alcohol to the branched chain 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 reacting until the viscosity (75 ℃) is 10000 +/-500 mPa.s, thereby obtaining a polyester polyol product.
The raw materials of the adhesive for food packaging comprise, by weight, 48 parts of polyester polyol, 27 parts of diisocyanate, 3 parts of a chain extender, 0.1 part of a catalyst and 6 parts of a 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 dibutyltin 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 1.5h 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;
and S4, adding deionized water (the adding 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.
This example provides the use of a polyester polyol in an adhesive for food packaging.
The polyester polyol comprises the following raw materials in parts by weight: 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 purified terephthalic acid and is derived from the petrifaction of a raisin.
The aliphatic dibasic acid is adipic acid; the melting point of adipic acid was 152 ℃ and the flash point was 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 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 reacting until the viscosity (75 ℃) is 10000 +/-500 mPa.s, thereby obtaining a polyester polyol product.
The raw materials of the adhesive for food packaging comprise, by weight, 48 parts of polyester polyol, 27 parts of diisocyanate, 3 parts of a chain extender, 0.1 part of a catalyst and 6 parts of a 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 dibutyltin 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 1.5h 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;
and S4, adding deionized water (the adding 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.
This example provides the use of a polyester polyol in an adhesive for food packaging.
The polyester polyol comprises the following raw materials in parts by weight: 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 purified terephthalic acid and is derived from the petrifaction of a raisin.
The aliphatic dibasic acid is adipic acid; the melting point of adipic acid was 152 ℃ and the flash point was 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 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 reacting until the viscosity (75 ℃) is 10000 +/-500 mPa.s to obtain a polyester polyol product.
The raw materials of the adhesive for food packaging comprise, by weight, 48 parts of polyester polyol, 27 parts of diisocyanate, 3 parts of a chain extender, 0.1 part of a catalyst and 6 parts of a 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 dibutyltin 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 1.5h 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;
and S4, adding deionized water (the adding 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 adhesive for food packaging.
Comparative example 1.
The comparative example provides the application of polyester polyol in an adhesive for food packaging, and the specific implementation mode is the same as that of 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.
The comparative example provides the application of polyester polyol in an adhesive for food packaging, and the specific implementation mode is the same as that of example 1; the difference lies in that the diisocyanate is MDI and HDI, and the weight ratio of MDI and HDI is 1: 1.
performance test method
1. Physical and chemical indexes of polyester polyol
The polyester polyols obtained in examples 1 to 3 and comparative example 1 were tested for their physical and chemical properties, as shown in Table 1.
Wherein the hydroxyl number is determined by reference to ASTM D4274; moisture determination is made with reference to ASTM D4672.
2. Adhesive performance
(1) Adhesion: PP (polypropylene) films were laminated using the adhesives obtained in examples 1 to 3 and comparative examples 1 to 2, cured at 50 ℃ for 20 hours, cut into 200 mm. times.30 mm samples, and tested for T-peel strength and tensile strength of 100mm/min with reference to GB/T2791-1995; the results are shown in Table 2.
(2) Boiling resistance: the samples obtained in examples 1-3 and comparative examples 1-2 are placed at 121 ℃ for 40min, and the reduction rate delta of the T-shaped peeling strength is calculated; defining that delta is less than or equal to 10 percent as qualified, and defining that delta is more than 10 percent as unqualified; the results are shown in Table 2.
Performance test data
Table 1.
Figure BDA0003318404050000081
TABLE 2
Figure BDA0003318404050000082

Claims (10)

1. The application of polyester polyol in the adhesive for food packaging is characterized in that the polyester polyol accounts for 40-68 wt% of the total weight of raw materials of the adhesive for food packaging.
2. The use of a polyester polyol in an adhesive for food packaging as claimed in claim 1, wherein said polyester polyol has a hydroxyl value of 25 to 70mgKOH/g, a solid content of 60 to 75 wt% and a moisture content of 300ppm or less.
3. The use of a polyester polyol in an adhesive for food packaging according to claim 1 or 2, wherein 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 (5-7): (2-6).
4. Use of a polyester polyol in an adhesive for food packaging according to claim 3, wherein said dibasic acid comprises an aromatic dibasic acid and/or an aliphatic dibasic acid.
5. The use of a polyester polyol in an adhesive for food packaging according to claim 4, wherein said dibasic acid comprises at least an aromatic dibasic acid having 2 carboxyl groups in ortho, meta or para distribution.
6. The use of a polyester polyol in an adhesive for food packaging as claimed in claim 5, wherein said dibasic acid comprises at least an aliphatic dibasic acid, said aliphatic dibasic acid comprising a linear aliphatic dibasic acid having a melting point of 102-184 ℃.
7. Use of a polyester polyol in an adhesive for food packaging according to any of claims 3 to 6, wherein the diols comprise linear diols and branched diols, the weight ratio of linear diols to branched diols being (0.2 to 3): (1-4).
8. Use of a polyester polyol in an adhesive for food packaging according to claim 7, wherein said linear diol comprises one or more combinations of 1, 4-butanediol, ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 6-hexanediol, 1, 7-heptanediol.
9. The use of a polyester polyol in an adhesive for food packaging as claimed in any one of claims 1 to 8, wherein the raw materials of the adhesive for food packaging comprise, by weight, 36 to 54 parts of polyester polyol, 20 to 30 parts of diisocyanate, 1 to 8 parts of chain extender, and 2 to 12 parts of solvent.
10. Use of a polyester polyol according to claim 6 in adhesives for food packaging, characterized in that the polyester polyol is prepared by the steps of: and mixing and reacting the aromatic dibasic acid, the branched chain dihydric alcohol, the aliphatic dibasic acid and the linear dihydric alcohol in sequence to obtain a polyester polyol finished product.
CN202111238513.2A 2021-10-25 2021-10-25 Application of polyester polyol in adhesive for food packaging Active CN115044020B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111238513.2A CN115044020B (en) 2021-10-25 2021-10-25 Application of polyester polyol in adhesive for food packaging

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111238513.2A CN115044020B (en) 2021-10-25 2021-10-25 Application of polyester polyol in adhesive for food packaging

Publications (2)

Publication Number Publication Date
CN115044020A true CN115044020A (en) 2022-09-13
CN115044020B CN115044020B (en) 2023-11-03

Family

ID=83156669

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111238513.2A Active CN115044020B (en) 2021-10-25 2021-10-25 Application of polyester polyol in adhesive for food packaging

Country Status (1)

Country Link
CN (1) CN115044020B (en)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09309939A (en) * 1996-05-23 1997-12-02 Dainippon Ink & Chem Inc Polyurethane resin composition and its production
KR20010055924A (en) * 1999-12-13 2001-07-04 백정호, 찰스 에프 놋트 Humidity-curing polyurethane adhesive
JP2004115681A (en) * 2002-09-27 2004-04-15 Toyo Ink Mfg Co Ltd Solventless adhesive composition and its use
CN101544880A (en) * 2009-03-12 2009-09-30 中山市康和化工有限公司 Adhesive for soft package compound and preparation method thereof
CN102212180A (en) * 2011-04-29 2011-10-12 黎明化工研究院 Microcellular polyurethane elastomer and preparation method thereof
CN102492113A (en) * 2011-12-01 2012-06-13 山西省应用化学研究所 Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI)
CN103305177A (en) * 2013-07-12 2013-09-18 天津克拉徳科技有限公司 Preparation method of single-component polyurethane adhesive
CN104232005A (en) * 2014-09-28 2014-12-24 东莞宏石功能材料科技有限公司 Polyurethane hot melt adhesive with high thermal resistance and preparation method of polyurethane hot melt adhesive
CN105330817A (en) * 2015-11-30 2016-02-17 东莞宏石功能材料科技有限公司 Water-proof moisture-permeable polyurethane thermoplasticity elastomer and preparation method thereof
CN105482762A (en) * 2015-12-02 2016-04-13 北京高盟新材料股份有限公司 Preparation method of reversed composite adhesive for food packaging
CN106833487A (en) * 2017-01-19 2017-06-13 湖州倍格曼新材料股份有限公司 A kind of high initial bonding strength polyurethane composite gel and preparation method thereof
CN108424510A (en) * 2018-03-22 2018-08-21 上海联景高分子材料有限公司 The preparation method of polyester polyol for adhesive for laminated film
CN111057512A (en) * 2019-12-30 2020-04-24 北京华腾新材料股份有限公司 Bi-component polyurethane adhesive for steam-resistant aluminum-plastic composite and preparation method thereof
CN111234760A (en) * 2020-03-11 2020-06-05 上海良基化工有限公司 High-performance adhesive
CN111995731A (en) * 2020-09-10 2020-11-27 浙江华峰热塑性聚氨酯有限公司 Polyester type thermoplastic elastomer

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09309939A (en) * 1996-05-23 1997-12-02 Dainippon Ink & Chem Inc Polyurethane resin composition and its production
KR20010055924A (en) * 1999-12-13 2001-07-04 백정호, 찰스 에프 놋트 Humidity-curing polyurethane adhesive
JP2004115681A (en) * 2002-09-27 2004-04-15 Toyo Ink Mfg Co Ltd Solventless adhesive composition and its use
CN101544880A (en) * 2009-03-12 2009-09-30 中山市康和化工有限公司 Adhesive for soft package compound and preparation method thereof
CN102212180A (en) * 2011-04-29 2011-10-12 黎明化工研究院 Microcellular polyurethane elastomer and preparation method thereof
CN102492113A (en) * 2011-12-01 2012-06-13 山西省应用化学研究所 Method for preparing waterborne polyurethane adhesive based on hexamethylene diisocyanate (HDI)-toluene diisocynate (TDI)
CN103305177A (en) * 2013-07-12 2013-09-18 天津克拉徳科技有限公司 Preparation method of single-component polyurethane adhesive
CN104232005A (en) * 2014-09-28 2014-12-24 东莞宏石功能材料科技有限公司 Polyurethane hot melt adhesive with high thermal resistance and preparation method of polyurethane hot melt adhesive
CN105330817A (en) * 2015-11-30 2016-02-17 东莞宏石功能材料科技有限公司 Water-proof moisture-permeable polyurethane thermoplasticity elastomer and preparation method thereof
CN105482762A (en) * 2015-12-02 2016-04-13 北京高盟新材料股份有限公司 Preparation method of reversed composite adhesive for food packaging
CN106833487A (en) * 2017-01-19 2017-06-13 湖州倍格曼新材料股份有限公司 A kind of high initial bonding strength polyurethane composite gel and preparation method thereof
CN108424510A (en) * 2018-03-22 2018-08-21 上海联景高分子材料有限公司 The preparation method of polyester polyol for adhesive for laminated film
CN111057512A (en) * 2019-12-30 2020-04-24 北京华腾新材料股份有限公司 Bi-component polyurethane adhesive for steam-resistant aluminum-plastic composite and preparation method thereof
CN111234760A (en) * 2020-03-11 2020-06-05 上海良基化工有限公司 High-performance adhesive
CN111995731A (en) * 2020-09-10 2020-11-27 浙江华峰热塑性聚氨酯有限公司 Polyester type thermoplastic elastomer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
张晓红;丁培;项尚林;王庭慰;王银叶;: "新型聚氨酯固化剂的制备", 包装工程, no. 02 *
林星;胡佳;蔡海元;崔爱玲;林中祥;: "PP或PE用双组分PU胶粘剂的制备与性能研究", 中国胶粘剂, no. 12 *
牛杰峰;朱长春;唐亚夫;詹中贤;: "油墨用热塑性聚氨酯弹性体的研制", 中国胶粘剂, no. 08 *

Also Published As

Publication number Publication date
CN115044020B (en) 2023-11-03

Similar Documents

Publication Publication Date Title
JP4197838B2 (en) Polyurethane adhesive
CN108884207B (en) Two-component solvent-free adhesive composition and method for producing the same
US4206299A (en) Adhesive composition
JP4823460B2 (en) Monomer-free reactive polyurethane adhesive reinforcement
EP2791195B1 (en) Ester carbonate polyols for hydrolitically stable adhesives
TWI421320B (en) Adhesive composition and laminate
KR100812932B1 (en) Moisture-hardening hot-melt adhesives, method for the production and the use thereof
JP4771276B2 (en) Laminating adhesive
CN111057511B (en) Bi-component polyurethane adhesive and preparation method thereof
CN112839976A (en) Hot melt adhesive composition comprising bio-based polyester polyols
JPH06116542A (en) Adhesive composition
EP2635618A1 (en) Two-component polyurethane adhesives with i tropic effect
CN113004502A (en) Method for producing polyester polyols and polyurethanes
CA1166395A (en) Composition for polyurethane adhesives
CN115044020B (en) Application of polyester polyol in adhesive for food packaging
JPH0349314B2 (en)
CN114163971A (en) PUR hot melt adhesive and preparation method thereof
TWI822673B (en) Moisture-curable polyurethane hot-melt resin composition
CN115651590B (en) Solvent-free polyurethane adhesive for industrial conveyor belt and preparation method thereof
KR20010053584A (en) Monomer-poor polyurethane bonding agent having an improved lubricant adhesion
JPH08269428A (en) Adhesive composition for laminate and production of laminated film
JPH0762128B2 (en) adhesive
CN110607159A (en) Hydrolysis-resistant polyester polyol, polyurethane prepared from hydrolysis-resistant polyester polyol, and preparation method and application of polyurethane
TWI834600B (en) Two-component solventless adhesive compositions and methods of making same
JPS636075A (en) Polyurethane adhesive composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant