CN115073715A - Polyester polyol for adhesive, and preparation method and application thereof - Google Patents
Polyester polyol for adhesive, and preparation method and application thereof Download PDFInfo
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- CN115073715A CN115073715A CN202111232280.5A CN202111232280A CN115073715A CN 115073715 A CN115073715 A CN 115073715A CN 202111232280 A CN202111232280 A CN 202111232280A CN 115073715 A CN115073715 A CN 115073715A
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- polyol
- polyester polyol
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- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 69
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 71
- 150000003077 polyols Chemical class 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 235000013305 food Nutrition 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 150000004715 keto acids Chemical class 0.000 claims abstract description 12
- 238000009459 flexible packaging Methods 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 9
- -1 aliphatic polyol Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 125000005472 straight-chain saturated fatty acid group Chemical group 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000014787 Vitis vinifera Nutrition 0.000 description 3
- 240000006365 Vitis vinifera Species 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- BAJISODJARYQDB-UHFFFAOYSA-N 1-(oxiran-2-yl)butane-2,3-diol Chemical compound CC(O)C(O)CC1CO1 BAJISODJARYQDB-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to the technical field of IPC 08G63/00, in particular to polyester polyol for an adhesive and a preparation method and application thereof. The raw materials comprise the following components in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 40-75: 15-60 parts. The polyester polyol with controllable hydroxyl value and viscosity can be obtained, and a feasible raw material basis is further provided for preparing the adhesive with high bonding strength, high peeling strength and strong boiling resistance; the water content and acid value of the polyester polyol are extremely low, so that the problems that the polyester polyol is easy to absorb moisture and is not easy to use in the adhesive for food flexible packaging are solved; the obtained polyester polyol with the specific structure can keep stronger peel strength for a flexible base material, can meet different requirements of downstream products, can be directly put into use, can be diluted according to conditions to facilitate subsequent operation, and provides a brand new choice for the adhesive for food flexible packaging.
Description
Technical Field
The invention relates to the technical field of IPC 08G63/00, in particular to polyester polyol for an adhesive and a preparation method and application thereof.
Background
Polyester polyol is a high molecular compound formed by esterifying polyol and polybasic acid at high temperature and then polycondensing, and is an important raw material for polyurethane synthesis due to high density of polar groups in molecules and high cohesive strength; meanwhile, with different molecular structures of polyester polyol, the obtained downstream product can be applied to various fields such as adhesives, foams, plates and the like. Wherein, the adhesive for food flexible package puts higher performance requirements on the polyester polyol because the adhesive is directly contacted with food and the substrate is soft. The traditional polyester polyol is easy to absorb moisture, has single solid content and poor controllability of indexes such as acid value, hydroxyl value and the like, and cannot meet the use requirement of the adhesive for food flexible packaging.
Chinese patent CN200610020398.0 discloses a preparation method of a polyester material for a high-shrinkage film, which uses purified terephthalic acid, ethylene glycol monomers and neopentyl glycol to jointly act to prepare the polyester material for the high-shrinkage film, so as to obtain the polyester material with high shrinkage rate and low cost.
Chinese patent CN200910048022.4 discloses a preparation method of non-crystalline polyester polyol for preparing thermosetting adhesive, which mixes terephthalic acid, phthalic acid or isophthalic acid with adipic acid AA, ethylene glycol EG or neopentyl glycol to obtain polyester with a specific soft segment structure under the action of a non-metal catalyst, solves the problems of complex process and high pollution in the existing polyester synthesis, and achieves the non-crystalline effect. The technology aims to optimize the polyester synthesis process, and the obtained product can not meet the use requirement of the adhesive for food flexible packaging.
Chinese patent CN201910481378.0 discloses a preparation method of a composite functional adhesive for food flexible packaging, which adopts phthalic anhydride polyester polyol with a hydroxyl value of 220-270, neopentyl glycol polyester polyol with a hydroxyl value of 53-59 and diethylene glycol polyester polyol with a hydroxyl value of 50-70 to react with MDI to obtain the adhesive with good barrier property suitable for food packaging. However, the technology has extremely high requirements on the performance of raw materials (various polymer raw materials with specific hydroxyl values are adopted), has poor feasibility in actual use, and is not suitable for being widely popularized in the technical field of adhesives for food flexible packaging.
Under the background, the research of polyester polyol which is safe, environment-friendly, controllable in performance index and high in bonding strength is an urgent problem to be solved in the field.
Disclosure of Invention
The invention provides the polyester polyol for the adhesive, solves the problems that the adhesive for food flexible packaging in the prior art has poor bonding performance and the index of the polyester polyol is difficult to control, and realizes the polyester polyol which is safe, environment-friendly, controllable in performance index and high in bonding strength.
In order to solve the above problems, a first aspect of the present invention provides a polyester polyol for adhesives, which comprises the following raw materials in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 40-75: 15-60.
In some preferred embodiments, the functionality of both the polyacid and the polyol is from 1 to 4.
Further preferably, the functionality of both the polyacid and the polyol is 2.
In some preferred embodiments, the polyatomic oxoacid includes an aliphatic polyatomic oxoacid and/or an aromatic polyatomic oxoacid.
In order to ensure that the polyester polyol has controllable hydroxyl value, color, moisture and other characteristics, and to the maximum extent meets the use requirement of the downstream adhesive, in some preferred embodiments, the multiple oxyacid comprises a first multiple oxyacid and a second multiple oxyacid, and the weight ratio of the first multiple oxyacid to the second multiple oxyacid is (0.5-2): 1.
in some preferred embodiments, the first polybasic oxoacid is a linear saturated fatty acid having a carbon chain length of 5 to 14.
In some preferred embodiments, the linear saturated fatty acid having a carbon chain length of 5 to 14 comprises a combination of one or more of adipic acid, 1, 8-octanedioic acid, azelaic acid, brassylic acid, and lauric acid.
In order to reduce the water content of the polyester polyol, promote the subsequent reaction stability of the polyester polyol and improve the boiling resistance of the adhesive product, it is further preferable that the linear saturated fatty acid with the carbon chain length of 5 to 14 comprises one or more of the combination of adipic acid, 1, 8-suberic acid and azelaic acid.
In some preferred embodiments, the second poly oxo acid is an aromatic poly oxo acid, and the aromatic poly oxo acid comprises at least one of phthalic acid, isophthalic acid, and terephthalic acid.
In order to improve the interface bonding force between the adhesive and the base material, the acid value (calculated by potassium hydroxide) of the terephthalic acid is more preferably 675 +/-2 mg/g, the content of the p-toluic acid is less than or equal to 150mg/kg, the ignition residue is less than or equal to 6mg/kg, and the water content is less than or equal to 0.2 wt%.
To promote the reactivity of the polyacid and the polyol, and in some preferred embodiments, the polyol comprises a first polyol and a second polyol, the weight ratio of the first polyol to the second polyol being (5-25): (15-35).
In some preferred embodiments, the first polyol is a linear aliphatic polyol having a melting point of-20 to 30 ℃, a boiling point of 180 to 260 ℃, and test conditions of 101.3 kPa.
In some preferred embodiments, the linear aliphatic polyol comprises a combination of one or more of 1, 4-butanediol, ethylene glycol, diethylene glycol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 5-pentanediol, 1, 7-heptanediol, propylene glycol.
In order to make the adhesive have stronger penetrability while maintaining adhesive strength, it is further preferred that the linear aliphatic polyol comprises one or more of 1, 4-butanediol, ethylene glycol, and diethylene glycol. The invention discovers that the molecular structure of the polyester polyol can be effectively regulated and controlled by adopting the specific straight-chain aliphatic polyol and the branched-chain aliphatic polyol which are matched together, and the wettability of the adhesive on the surface of the base material is further improved, so that the adhesive not only can be applied to rigid and smooth base materials, but also can be applied to the adhesion of soft, light and thin food flexible packages.
In order to reduce the acid value of the polyester polyol and improve the processability of the product, in some preferred embodiments, the second polyol is a branched aliphatic polyol having a weight ratio of primary, secondary, tertiary, and quaternary carbons of (1-5): (1-6): (0-4): (0-2).
In some preferred embodiments, the weight ratio of the aromatic poly oxo acid to the branched aliphatic polyol is (25-35): (15-35).
In some preferred embodiments, the branched aliphatic polyol comprises a combination of one or more of 2, 2-dimethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, glycidylpropylene glycol, 1,1, 1-tris (hydroxymethyl) propane.
To further enhance the bonding of the adhesive to food grade packaging materials, and to reduce the tendency of the adhesive product to warp, in some preferred embodiments, the branched chain-containing aliphatic polyol comprises a combination of one or more of 2, 2-dimethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, and glycidol and dipropylene glycol.
In order to control the molecular structure of the polyester polyol to have suitable polarity, it is further preferred that the branched aliphatic polyol is 2, 2-dimethyl-1, 3-propanediol and 2-methyl-1, 3-propanediol, and the molar ratio of 2, 2-dimethyl-1, 3-propanediol and 2-methyl-1, 3-propanediol is (6 to 14): 1; the optimal choice is 9: 1.
the second aspect of the present invention provides a method for preparing a polyester polyol for an adhesive, comprising the steps of: adding the polybasic oxyacid and the polyhydroxy compound into a reaction kettle, and reacting at the temperature of 140-.
In some preferred embodiments, the preparing step comprises: adding the second polybasic oxyacid, the second polyhydroxy compound, the first polybasic oxyacid and the first polyhydroxy compound into a reaction kettle in sequence, and reacting at the temperature of 140-.
Further preferably, the preparation step comprises:
s1, adding a second polybasic oxyacid and a second polyhydroxy compound into a reaction kettle, heating to 180-190 ℃, reacting until the acid value is 20 +/-5, and cooling;
s2, cooling to 70-90 ℃, sequentially adding the first polybasic oxoacid and the first polyhydroxy compound into a reaction kettle, heating to 140-;
the finished product can be directly discharged and packaged, and can also be diluted to a certain solid content by adding a solvent so as to reduce the viscosity and facilitate subsequent gluing operation. The prepared small molecular polyester finished product can be added into a reaction vessel for viscosity reduction according to the use condition of downstream products.
The dilution method is a method commonly used in the art, and is not particularly limited, for example, dilution with ethyl acetate is added.
In some preferred embodiments, the hydroxyl value of the polyester polyol prepared by the invention can be accurately controlled to be 30-60 mgKOH/g, and the hydroxyl value of the diluted polyester polyol can be accurately controlled to be 20-45 mgKOH/g, so that a convenient scheme is provided for further preparing an adhesive subsequently.
In the process of researching the polyester polyol, the aliphatic polybasic oxyacid and the aromatic polybasic oxyacid are added and react with the polyhydroxy compound together, so that the reaction activity of the polyester polyol can be obviously improved, and the bonding strength of the adhesive is further improved. The inventor further finds that the linear saturated aliphatic oxyacid and the aromatic binary oxyacid with the carbon chain length of 5-14 act, and the weight ratio is set as (0.5-2): 1, polyester molecular chains obtained by reaction with the composite polyhydroxy compound have low moisture, the controllability of hydroxyl values of products is strong, and the prepared adhesive has high peeling strength and can provide a stable interface adhesive effect particularly for flexible and soft materials; the inventor also finds that when the polyol selects straight-chain aliphatic polyol to react with branched-chain aliphatic polyol and the compounded polybasic oxyacid, polyester polyol with extremely low water content and acid value can be obtained, and the boiling resistance of the applied adhesive is obviously improved; it has been unexpectedly found that the branched aliphatic polyol is present in a molar ratio of (6-14): 1 (especially 9: 1) of 2, 2-dimethyl-1, 3-propanediol and 2-methyl-1, 3-propanediol, and the polyester polyol formed with dibasic acid can have a water content as low as 300ppm and an acid value as low as 1mgKOH/g or less.
In the exploration process, the invention also discovers that the performance of the polyester polyol is greatly influenced by the mixing sequence and the process conditions of the raw materials, and further influences the bonding effect of the downstream adhesive. After a great deal of trial and study, it is found that firstly, aromatic polybasic oxyacid and specific branched chain-containing aliphatic polyol are mixed and reacted until the acid value reaches about 15-25 to form an intermediate product, then, linear saturated fatty acid and linear aliphatic polyol are added to react with the intermediate product to obtain polyester polyol which has a proper molecular chain structure and can keep the reaction activity and the cohesion, and the applied adhesive is particularly suitable for bonding food-grade packaging materials, particularly for PE, PET, AL and CPP base materials, can exert lasting separation resistance, can exert packaging and sealing effects for a long time, and prevents foods from being affected with moisture, deteriorated, damaged, corroded and the like.
The third aspect of the invention provides a preparation method of polyester polyol for an adhesive, and the polyester polyol is applied to the adhesion of food flexible packages.
Has the advantages that:
the polyester polyol for the adhesive provided by the invention has the following advantages:
(1) the polyester polyol has the advantages of safe and environment-friendly raw materials and simple and convenient process steps, can obtain the polyester polyol with controllable hydroxyl value and viscosity on the basis of higher scheme feasibility, and further provides a feasible raw material basis for preparing the adhesive with high bonding strength, high peel strength and strong boiling resistance;
(2) aliphatic dibasic acid and aromatic dibasic acid are adopted to react with straight chain dihydric alcohol and branched chain-containing dihydric alcohol to obtain polyester polyol with extremely low water content and acid value under a specific reaction sequence, so that the problems that the polyester polyol is easy to absorb moisture and is not easy to use in an adhesive for food flexible packaging are solved; the obtained polyester polyol with the specific structure can keep stronger peel strength and excellent bonding property for flexible base materials such as PE, PET, AL, CPP and the like.
(3) The polyester polyol obtained by the invention can be used as a bio-based raw material to improve the environmental protection safety of products, can meet different requirements of downstream products, can be directly put into use, can be diluted according to conditions to facilitate subsequent operation, and provides a brand new choice for the adhesive for food flexible packaging.
Detailed Description
Example 1.
The invention provides polyester polyol for an adhesive, which comprises the following raw materials in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 60: 40.
the polybasic oxyacid comprises a first polybasic oxyacid and a second polybasic oxyacid, and the weight ratio of the first polybasic oxyacid to the second polybasic oxyacid is 1: 1.
the first polybasic oxyacid is straight-chain saturated fatty acid, the straight-chain saturated fatty acid is azelaic acid, and the CAS number is 123-99-9.
The second polybasic oxyacid is purified terephthalic acid and is derived from the petrifaction of a Chinese raisin.
The polyol comprises a first polyol and a second polyol, the weight ratio of the first polyol to the second polyol is 15: 25.
the first polyol is a linear aliphatic polyol, the linear aliphatic polyol is 1, 4-butanediol, the 1, 4-butanediol has a melting point of 16 ℃ and a boiling point of 230 ℃ (test conditions of 101.3 kPa).
The branched chain-containing aliphatic polyol is 2, 2-dimethyl-1, 3-propanediol (CAS number: 126-30-7) and 2-methyl-1, 3-propanediol (CAS number: 2163-42-0); the molar ratio of 2, 2-dimethyl-1, 3-propanediol to 2-methyl-1, 3-propanediol is 9: 1.
in a second aspect, this embodiment provides a method for preparing a polyester polyol for an adhesive, comprising the steps of:
s1, adding a second polybasic oxyacid and a second polyhydroxy compound into a reaction kettle, heating to 185 ℃, reacting until the acid value is 20 +/-1, and cooling;
s2, cooling to 80 ℃, sequentially adding a first polybasic oxyacid and a first polyhydroxy compound into a reaction kettle, heating to 150 ℃, vacuumizing to react until the viscosity is 8000-12000 mPa.s, and breaking vacuum to cool to obtain a finished product; in a third aspect, this example provides a method for preparing a polyester polyol for use in bonding flexible food packaging.
Example 2.
The invention provides polyester polyol for an adhesive, which comprises the following raw materials in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 60: 40.
the polybasic oxyacid comprises a first polybasic oxyacid and a second polybasic oxyacid, and the weight ratio of the first polybasic oxyacid to the second polybasic oxyacid is 1: 1.
the first polybasic oxyacid is straight-chain saturated fatty acid, the straight-chain saturated fatty acid is 1, 8-octanedioic acid, and the CAS number is 111-20-6.
The second polybasic oxyacid is purified terephthalic acid and is derived from the petrifaction of a Chinese raisin.
The polyol comprises a first polyol and a second polyol, the weight ratio of the first polyol to the second polyol is 15: 25.
the first polyol is a linear aliphatic polyol, the linear aliphatic polyol is 1, 4-butanediol, the 1, 4-butanediol has a melting point of 16 ℃ and a boiling point of 230 ℃ (test conditions of 101.3 kPa).
The branched chain-containing aliphatic polyol is 2, 2-dimethyl-1, 3-propanediol (CAS number: 126-30-7) and 2-methyl-1, 3-propanediol (CAS number: 2163-42-0); the molar ratio of 2, 2-dimethyl-1, 3-propanediol to 2-methyl-1, 3-propanediol is 9: 1.
in a second aspect, this embodiment provides a method for preparing a polyester polyol for an adhesive, comprising the steps of:
s1, adding a second polybasic oxyacid and a second polyhydroxy compound into a reaction kettle, heating to 185 ℃, reacting until the acid value is 20 +/-1, and cooling;
s2, cooling to 80 ℃, sequentially adding a first polybasic oxyacid and a first polyhydroxy compound into a reaction kettle, heating to 150 ℃, vacuumizing to react until the viscosity is 8000-12000 mPa.s, and breaking vacuum to cool to obtain a finished product;
in a third aspect, this example provides a method for preparing a polyester polyol for use in bonding flexible food packaging.
Example 3.
The invention provides polyester polyol for an adhesive, which comprises the following raw materials in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 60: 40.
the polybasic oxyacid comprises a first polybasic oxyacid and a second polybasic oxyacid, and the weight ratio of the first polybasic oxyacid to the second polybasic oxyacid is 1: 1.
the first polybasic oxyacid is straight-chain saturated fatty acid, the straight-chain saturated fatty acid is azelaic acid, and the CAS number is 123-99-9.
The second polybasic oxyacid is purified terephthalic acid and is derived from the petrifaction of a Chinese raisin.
The polyol comprises a first polyol and a second polyol, the weight ratio of the first polyol to the second polyol is 15: 25.
the first polyol is a linear aliphatic polyol, the linear aliphatic polyol is 1, 4-butanediol, the 1, 4-butanediol has a melting point of 16 ℃ and a boiling point of 230 ℃ (test conditions of 101.3 kPa).
The branched chain-containing aliphatic polyol is 2, 2-dimethyl-1, 3-propanediol (CAS number: 126-30-7) and 2-methyl-1, 3-propanediol (CAS number: 2163-42-0); the molar ratio of 2, 2-dimethyl-1, 3-propanediol to 2-methyl-1, 3-propanediol is 9: 1.
in a second aspect, this embodiment provides a method for preparing a polyester polyol for an adhesive, comprising the steps of:
s1, adding a second polybasic oxyacid and a second polyhydroxy compound into a reaction kettle, heating to 185 ℃, reacting until the acid value is 20 +/-1, and cooling;
s2, cooling to 80 ℃, sequentially adding a first polybasic oxyacid and a first polyhydroxy compound into a reaction kettle, heating to 150 ℃, vacuumizing to react until the viscosity is 8000-12000 mPa.s, and breaking vacuum to cool to obtain a finished product;
in a third aspect, this example provides a method for preparing a polyester polyol for use in bonding flexible food packaging.
Comparative example 1.
The invention provides a polyester polyol for adhesive, the specific implementation mode is the same as that of example 1; except that the straight chain saturated fatty acid was tridecanedioic acid with CAS number 505-52-2.
Comparative example 2.
The first aspect of the invention provides a polyester polyol for adhesives, the specific embodiment is the same as example 1; with the difference that the weight ratio of the first polyol to the second polyol is 30: 10.
the polyester polyols of examples 1 to 3 and comparative examples 1 to 2 were prepared as follows:
note: represents the same starting material as in example 1.
Performance test
1. Appearance:
example 1 was a light yellow transparent liquid at 75 ℃.
2. Physical and chemical indexes
The polyester polyols of examples 1-5 and comparative examples 1-2 were tested for various indicators, as shown in the following table.
Claims (10)
1. The polyester polyol for the adhesive is characterized by comprising the following raw materials in parts by weight: a polybasic oxoacid and a polyol; the weight ratio of the polybasic oxyacid to the polyhydroxy compound is 40-75: 15-60 parts.
2. The polyester polyol for adhesives according to claim 1, wherein the functionalities of both the polybasic oxyacid and the polyhydroxy compound are 1 to 4.
3. The polyester polyol for adhesives according to claim 1 or 2, wherein the polybasic oxy acids include aliphatic polybasic oxy acids and/or aromatic polybasic oxy acids.
4. A polyester polyol for adhesives as claimed in any one of claims 1 to 3, wherein the polybasic oxy acids comprise a first polybasic oxy acid and a second polybasic oxy acid, and the weight ratio of the first polybasic oxy acid to the second polybasic oxy acid is (0.5 to 2): 1.
5. the polyester polyol for adhesives according to claim 4, wherein the first polybasic oxy acid is a linear saturated fatty acid, and the carbon chain length of the linear saturated fatty acid is 5 to 14.
6. A polyester polyol for adhesives according to any one of claims 1 to 5, wherein the polyol comprises a first polyol and a second polyol, and the weight ratio of the first polyol to the second polyol is (5-25): (15-35).
7. The polyester polyol for adhesives according to claim 6, wherein the first polyol is a linear aliphatic polyol having a melting point of-20 to 30 ℃ and a boiling point of 180 to 260 ℃.
8. The polyester polyol for adhesives according to claim 6 or 7, wherein the second polyol is a branched aliphatic polyol having a weight ratio of primary carbon, secondary carbon, tertiary carbon and quaternary carbon of (1 to 5): (1-6): (0-4): (0-2).
9. A method for preparing a polyester polyol for adhesives according to any one of claims 1 to 8, comprising the steps of: adding the polybasic oxyacid and the polyhydroxy compound into a reaction kettle for mixing, and reacting at the temperature of 140-.
10. Use of a polyester polyol for adhesives according to any of claims 1 to 8, wherein the polyester polyol is used for bonding food flexible packaging.
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