CN116535631B - Degradable copolyester hot melt adhesive and preparation method thereof - Google Patents
Degradable copolyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN116535631B CN116535631B CN202310402469.7A CN202310402469A CN116535631B CN 116535631 B CN116535631 B CN 116535631B CN 202310402469 A CN202310402469 A CN 202310402469A CN 116535631 B CN116535631 B CN 116535631B
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 93
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 49
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 27
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 24
- OWUTVCVPEOXXHD-UHFFFAOYSA-N trimethoxy(prop-1-enyl)silane Chemical compound CO[Si](OC)(OC)C=CC OWUTVCVPEOXXHD-UHFFFAOYSA-N 0.000 claims abstract description 24
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims description 45
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- 230000003078 antioxidant effect Effects 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 230000032050 esterification Effects 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 20
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 19
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000012153 distilled water Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 108700032845 Ala(2)- enkephalinamide-Met Proteins 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- -1 Polybutylene terephthalate Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the field of copolyester hot melt adhesives, in particular to a degradable copolyester hot melt adhesive and a preparation method thereof. The invention firstly synthesizes a degradable copolyester hot melt adhesive by taking terephthalic acid, itaconic acid, dodecanedioic acid, diglycol and 1,4 butanediol as raw materials, and in order to further improve the adhesive property and mechanical property, the invention further adds propenyl trimethoxysilane and trimesic acid in the polycondensation reaction process, thereby greatly improving the adhesive property and mechanical property.
Description
Technical Field
The invention relates to the field of copolyester hot melt adhesives, in particular to a degradable copolyester hot melt adhesive and a preparation method thereof.
Background
Hot Melt Adhesives (HMA) are solvent free thermoplastic solid materials, mainly obtained by melt blending thermoplastic resins or thermoplastic elastomers with other components. It is a solid at low temperatures (less than 82 ℃) and a low viscosity melt at high temperatures (above 82 ℃). Can be quickly solidified after cooling to form firm bonding. HMA exhibits various good mechanical properties and physical functions compared to other adhesives, such as traditional solvent-based adhesives. They form a strong and durable bond after rapid cooling. In addition, HMA technology also presents a number of unique advantages over other adhesives in processing and use, including reduced cost, removal of Volatile Organic Compound (VOC) emissions in the production process, elimination of the risk of explosion of solvent-based adhesives, removal of dryers in the production line, and simplicity of operation of the various substrates or conditions.
Currently, in the aspect of application of hot melt adhesives in industry, the hot melt adhesives can be classified into: the main groups include (1) polyurethane Type (TPU), (2) polyester type (PET), (3) ethylene-vinyl acetate copolymer (EVA), (4) polyamide type (PA), (5) polyolefin type (PO), and (6) acrylic copolymer (EEA).
The Polyester (PET) hot melt adhesive mainly comprises a copolyester polymer and an additive, and the polymer is regulated and controlled by the additive to obtain the PET hot melt adhesive with excellent performance and wide application range. The PET hot melt adhesives commonly used in the market generally produce good adhesion properties on the surfaces of rubber and metal articles at temperatures ranging from 110 to 130 ℃. Kim et al, in Polybutylene terephthalate modified with dimer acid methylester derived from fatty acid methyl esters and its use as a hot-melt adhesive, used methyl Dimer Acid (DAME) monomer, dimethyl terephthalate (DMT), dimethyl isophthalate (DMI) and 1, 4-Butanediol (BDO) as raw materials, which were prepared from Fatty Acid Methyl Esters (FAMEs) by Diels Alder reaction, and synthesized a series of polyester copolymers by melt polycondensation. Research shows that the polyester modified copolymer such as DAME has higher thermal stability, adjustable mechanical property and excellent adhesive property, can replace the application of HMA, and can even be compared favorably with petroleum-based commercial products. Therefore, the polyesters can provide higher thermal stability, adjustable mechanical properties and excellent adhesive properties, and are good candidates for hot melt adhesive materials.
With the continuous research and development of domestic and foreign experts on hot melt adhesives, the variety is increased, the performance of the hot melt adhesives is improved greatly, and the hot melt adhesives play an important role in a plurality of fields. Nowadays, with the deep penetration of environmental protection concepts, the development of the adhesive property and the service life are focused on the improvement of the conventional hot melt adhesives, such as EVA hot melt adhesives, polyurethane (PU) hot melt adhesives, and Polyamide (PA) hot melt adhesives. The novel hot melt adhesive is more preferable to degradable high polymer materials in the selection of the base materials of the hot melt adhesive while ensuring the adhesive performance.
The degradable polyester hot melt adhesive is a green material which is rapidly developed in recent years, can be degraded into harmless substances, avoids the problem of environmental pollution of the traditional hot melt adhesive, does not contain toxic and harmful substances, and is safe to use. In addition, the degradable polyester hot melt adhesive is similar to the traditional hot melt adhesive in processing technology, is easy to process and mold, and can control the degradation speed of the degradable polyester hot melt adhesive by adjusting the chemical bond and the structure in the polymer so as to adapt to different application requirements. However, the defect is that the performance of the existing degradable polyester hot melt adhesive is still to be improved, and the existing degradable polyester hot melt adhesive has limitations in the aspects of adhesion, tensile strength and the like compared with the traditional polyester hot melt adhesive.
In recent years, researchers have conducted extensive research on the development of degradable polyester hot melt adhesives. Among them, some researches have focused on synthetic methods of polyester hot melt adhesives, such as preparation of degradable polyester hot melt adhesives using biomass as a raw material, development of new degradable copolyesters, and the like. The bio-based polymer is obtained by polymerizing bio-based monomers extracted from natural products, such as corn starch, soy protein, etc., which are naturally derived and widely used in daily life. Common biomass such as lactic acid, starch, cellulose, proteins and amides have been developed and demonstrated as alternatives to petroleum-based hot melt adhesives. In the current research stage, the full-bio-based hot melt adhesive completely replaces the traditional hot melt adhesive and has a certain technical bottleneck, even if the full-bio-based hot melt adhesive can be successfully prepared, the full-bio-based hot melt adhesive is limited in the commercial market due to high production cost, and in addition, the adhesive property and the mechanical property of the full-bio-based hot melt adhesive have a larger gap compared with those of the traditional hot melt adhesive.
Therefore, it is necessary to develop and synthesize a degradable polyester hot melt adhesive with strong mechanical properties and adhesive properties. CN 107652420B discloses a preparation method of hot melt adhesive, which mainly comprises the following steps: (1) Adding dibasic acid formed by mixing terephthalic acid, isophthalic acid, sebacic acid and dodecanedioic acid, dihydric alcohol formed by mixing butanediol and 1, 3-propanediol and a catalyst into an esterification kettle according to a preset proportion for esterification reaction, wherein the reaction temperature is 160-205 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished; (2) Adding an antioxidant into the product obtained in the step (1), performing polycondensation reaction for 2.0h at 230-240 ℃ and 100-150 Pa, then introducing nitrogen to remove vacuum, and discharging while the product is hot. The copolyester hot melt adhesive directly prepared by the synthetic method disclosed by the invention has a good bonding effect in a certain aging period (such as 12 months), and can be rapidly degraded under natural conditions after exceeding the aging period. Its adhesive properties and mechanical properties are however to be improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a degradable copolyester hot melt adhesive and a preparation method thereof.
A preparation method of a degradable copolyester hot melt adhesive comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100: (120-160): (0.5-2), adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 160-180 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) Adding 90-110 parts of the prepolymer prepared in the step (1) and 0.1-1 part of an antioxidant into a reactor, heating to 190-230 ℃, decompressing to 100-200Pa, performing polycondensation reaction for 2-3h, introducing nitrogen to release vacuum, discharging while the mixture is hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:
(0.4-0.6): (0.4-0.8) and mixing.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of (0.2-0.5): 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is (0.5-0.8): 1.
the copolyester hot melt adhesive prepared by copolymerizing the dibasic acid and the dihydric alcohol has biodegradability, and the preparation method is simple and the production cost is low. The itaconic acid is adopted to replace the traditional dibasic acid, and the diglycol is adopted to replace the traditional dibasic alcohol, so that the adhesive property and toughness of the prepared degradable copolyester hot melt adhesive are improved. However, the adhesive properties and mechanical properties thereof are poor.
Therefore, further, the invention provides a preparation method of the degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100: (120-160): (0.5-2), adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 160-180 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) Adding 90-110 parts of the prepolymer prepared in the step (1), 1-5 parts of trimesic acid and 0.1-1 part of an antioxidant into a reactor, heating to 85-95 ℃ to react for 0.4-0.6h, heating to 190-230 ℃, decompressing to 100-200Pa to perform polycondensation reaction for 2-3h, introducing nitrogen to release vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:
(0.4-0.6): (0.4-0.8) and mixing.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of (0.2-0.5): 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is (0.5-0.8): 1.
according to the scheme, trimesic acid is further added in the prepolymer polycondensation reaction, and as the content of dihydric alcohol in the raw material of the esterification reaction in the step (1) is larger than that of the dihydric acid, the ester obtained by the esterification reaction contains a large amount of terminal hydroxyl groups, and can further react with the trimesic acid to form esterification crosslinking, so that a network structure is formed by taking the trimesic acid as a center, and the mechanical property of the trimesic acid is enhanced. However, the present invention has further found that the adhesive properties are still not ideal.
Therefore, the invention further provides a preparation method of the degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100: (120-160): (0.5-2), adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 160-180 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) Adding 90-110 parts of the prepolymer prepared in the step (1), 1-5 parts of propenyl trimethoxysilane, 1-5 parts of trimesic acid and 0.1-1 part of antioxidant into a reactor, heating to 85-95 ℃ to react for 0.4-0.6h, heating to 190-230 ℃, decompressing to 100-200Pa to perform polycondensation reaction for 2-3h, introducing nitrogen to remove vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:
(0.4-0.6): (0.4-0.8) and mixing.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of (0.2-0.5): 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is (0.5-0.8): 1.
the antioxidant in the step (2) is at least one of antioxidant 1010, antioxidant 164 and antioxidant TNP; preferably, the antioxidant is antioxidant TNP.
In the invention, propenyl trimethoxysilane and trimesic acid are simultaneously added in the polymerization reaction process of the prepolymer, and the prepolymer can further react with trimesic acid to form esterification crosslinking, so that a reticular structure is formed by taking trimesic acid as a center, and the mechanical property of the prepolymer is enhanced. Meanwhile, the raw materials contain propenyl trimethoxysilane, one end of the propenyl trimethoxysilane can be bonded with an inorganic surface, and the other end of the propenyl trimethoxysilane is bonded with an organic group, so that good combination of inorganic matters and organic matters is realized, and the bonding performance of the prepared hot melt adhesive is enhanced.
The invention has the beneficial effects that:
the invention firstly synthesizes a degradable copolyester hot melt adhesive by taking terephthalic acid, itaconic acid, dodecanedioic acid, diglycol and 1,4 butanediol as raw materials, and in order to further improve the adhesive property and mechanical property, the invention further adds propenyl trimethoxysilane and trimesic acid in the polycondensation reaction process, thereby greatly improving the adhesive property and mechanical property.
Detailed Description
Propenyl trimethoxysilane, CAS no: 2551-83-9.
Trimesic acid, CAS number: 554-95-0.
Antioxidant TNP, CAS number: 305-88-2, model: TNP.
Terephthalic acid, CAS number: 100-21-0.
Itaconic acid, CAS number: 97-65-4.
Dodecanedioic acid, CAS number: 693-23-2.
Diethylene glycol, CAS number: 111-46-6.
Dibutyl tin dilaurate, CAS number: 77-58-7.
Tetrabutyl titanate, CAS number: 5593-70-4.
Example 1
A preparation method of a degradable copolyester hot melt adhesive comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100:140:1, mixing, adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 170 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) And (3) adding 100 parts of the prepolymer prepared in the step (1) and 0.5 part of an antioxidant into a reactor according to parts by mass, heating to 210 ℃, decompressing to 150Pa, performing polycondensation reaction for 2 hours, introducing nitrogen, releasing vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:0.5: 0.6.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of 0.3: 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is 0.6:1.
and (3) the antioxidant in the step (2) is antioxidant TNP.
Example 2
The invention provides a preparation method of a degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100:140:1, mixing, adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 170 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) And (3) adding 100 parts of the prepolymer prepared in the step (1), 3 parts of trimesic acid and 0.5 part of an antioxidant into a reactor, heating to 90 ℃ for reaction for 0.5h, heating to 210 ℃, decompressing to 150Pa, carrying out polycondensation reaction for 2h, introducing nitrogen, releasing vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:0.5: 0.6.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of 0.3: 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is 0.6:1.
and (3) the antioxidant in the step (2) is antioxidant TNP.
Example 3
The invention provides a preparation method of a degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100:140:1, mixing, adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 170 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) And (3) adding 100 parts of the prepolymer prepared in the step (1), 3 parts of propenyl trimethoxysilane, 3 parts of trimesic acid and 0.5 part of antioxidant into a reactor, heating to 90 ℃ for reaction for 0.5h, heating to 210 ℃, reducing the pressure to 150Pa for polycondensation reaction for 2h, introducing nitrogen to release vacuum, discharging while the materials are hot, and granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:0.5: 0.6.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of 0.3: 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is 0.6:1.
and (3) the antioxidant in the step (2) is antioxidant TNP.
Example 4
The invention provides a preparation method of a degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100:140:1, mixing, adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 170 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) And (3) adding 100 parts of the prepolymer prepared in the step (1), 3 parts of propenyl trimethoxysilane and 0.5 part of an antioxidant into a reactor, heating to 90 ℃ for reaction for 0.5h, heating to 210 ℃, decompressing to 150Pa, carrying out polycondensation reaction for 2h, introducing nitrogen, releasing vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:0.5: 0.6.
The dihydric alcohol in the step (1) is prepared from diethylene glycol and 1,4 butanediol according to the molar ratio of 0.3: 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is 0.6:1.
and (3) the antioxidant in the step (2) is antioxidant TNP.
Comparative example 1
The invention provides a preparation method of a degradable copolyester hot melt adhesive, which comprises the following steps:
(1) The molar ratio of the dibasic acid to the dihydric alcohol to the catalyst is 100:140:1, mixing, adding the mixture into an esterification kettle for esterification reaction, wherein the reaction temperature is 170 ℃, and when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, ending the esterification reaction to obtain a prepolymer;
(2) And (3) adding 100 parts of the prepolymer prepared in the step (1), 3 parts of propenyl trimethoxysilane, 3 parts of trimesic acid and 0.5 part of antioxidant into a reactor, heating to 90 ℃ for reaction for 0.5h, heating to 210 ℃, reducing the pressure to 150Pa for polycondensation reaction for 2h, introducing nitrogen to release vacuum, discharging while the materials are hot, and granulating and drying to obtain the degradable copolyester hot melt adhesive.
The dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1:0.5: 0.6.
The dihydric alcohol in the step (1) is prepared from ethylene glycol and 1,4 butanediol according to the mole ratio of 0.3: 1.
The catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is 0.6:1.
and (3) the antioxidant in the step (2) is antioxidant TNP.
Test example 1
Peel strength test standard: GB/T2790-1995 method for testing 180-degree peel Strength of Adhesives Flexible Material to rigid Material
Table 1: peel strength of the degradable copolyester hot melt adhesive prepared in each example and comparative example
| Peel strength N/5cm | |
| Example 1 | 26.5 |
| Example 2 | 28.8 |
| Example 3 | 32.4 |
| Example 4 | 30.9 |
It can be seen from Table 1 that the peel strength of the degradable copolyester hot melt adhesive prepared in example 3 of the present invention is the greatest, indicating that it has the greatest adhesive property. The invention is characterized in that propenyl trimethoxy silane and trimesic acid are simultaneously added in the polymerization reaction process of the prepolymer, and the prepolymer can further react with trimesic acid to form esterification crosslinking, so that a reticular structure is formed by taking trimesic acid as a center, and the mechanical property of the prepolymer is enhanced. Meanwhile, the raw materials contain propenyl trimethoxysilane, one end of the propenyl trimethoxysilane can be bonded with an inorganic surface, and the other end of the propenyl trimethoxysilane is bonded with an organic group, so that good combination of inorganic matters and organic matters is realized, and the bonding performance of the prepared hot melt adhesive is enhanced. The reduction in peel strength of the propenyl trimethoxysilane alone of example 4 was not significant compared to example 3, indicating that it is propenyl trimethoxysilane that primarily enhances its bond strength. The peel strength of the degradable copolyester hot melt adhesive prepared in the example 2 is obviously reduced compared with that of the example 3, which shows that the adhesive property is greatly reduced, but the adhesive property is slightly improved compared with that of the example 1, and the invention considers that the trimesic acid improves the mechanical property of the hot melt adhesive and also improves the adhesive property to a certain extent, but the effect is weaker than that of propenyl trimethoxysilane.
Test example 2
Elongation at break test: GB/T1040.1-2018 determination of tensile Properties of plastics part 1: general rules (general rules)
Table 2: mechanical Properties of the degradable copolyester Hot melt adhesive prepared in each example and comparative example
| Elongation at break/% | |
| Example 1 | 184 |
| Example 2 | 351 |
| Example 3 | 364 |
| Example 4 | 186 |
| Comparative example 1 | 214 |
As can be seen from Table 2, the degradable copolyester hot melt adhesive prepared in example 3 has the greatest elongation at break, indicating that it has the best toughness. The invention is characterized in that propenyl trimethoxy silane and trimesic acid are simultaneously added in the polymerization reaction process of the prepolymer, and the prepolymer can further react with trimesic acid to form esterification crosslinking, so that a reticular structure is formed by taking trimesic acid as a center, and the mechanical property of the prepolymer is enhanced. Meanwhile, the raw materials contain propenyl trimethoxysilane, one end of the propenyl trimethoxysilane can be bonded with an inorganic surface, and the other end of the propenyl trimethoxysilane is bonded with an organic group, so that good combination of inorganic matters and organic matters is realized, and the bonding performance of the prepared hot melt adhesive is enhanced. The degradable copolyester hot melt adhesive prepared in example 4 has obviously reduced elongation at break compared with that of example 3, which shows that the reaction of the prepolymer and trimesic acid to form an esterified crosslinked network structure is a main factor for improving the toughness of the hot melt adhesive. The elongation at break of the degradable copolyester hot melt adhesive prepared in the example 2 is slightly reduced compared with that of the example 3, and the invention speculates that the degradable copolyester hot melt adhesive is improved in toughness due to the fact that the propenyl trimethoxysilane contains vinyl bonds, the raw material adopted by the hot melt adhesive prepolymer contains itaconic acid which also contains vinyl bonds, and the hot melt adhesive is possibly crosslinked under the hot melt condition, but the improvement is not obvious due to the higher vinyl crosslinking reaction condition. As can be seen from comparison of comparative example 1 and example 3, another major factor of the excellent toughness of the degradable copolyester hot melt adhesive prepared by the invention is that diethylene glycol is contained in the raw material of the prepolymer, and the diethylene glycol can enhance the toughness of the polymer molecular chain due to the ether bond, so that the degradable copolyester hot melt adhesive prepared by the invention has extremely strong toughness.
Claims (5)
1. The preparation method of the degradable copolyester hot melt adhesive is characterized by comprising the following steps of:
(1) Mixing dibasic acid, dihydric alcohol and a catalyst, and adding the mixture into an esterification kettle for esterification reaction to obtain a prepolymer;
(2) Adding the prepolymer prepared in the step (1), propenyl trimethoxysilane, trimesic acid and an antioxidant into a reactor, heating to 85-95 ℃ to react for 0.4-0.6h, then carrying out polycondensation reaction, introducing nitrogen to release vacuum, discharging while the materials are hot, granulating and drying to obtain the degradable copolyester hot melt adhesive;
the dibasic acid in the step (1) is prepared from terephthalic acid, itaconic acid and dodecanedioic acid according to the mol ratio of 1: (0.4-0.6): (0.4-0.8) mixing;
the dihydric alcohol in the step (1) is prepared from diglycol and 1, 4-butanediol according to the mol ratio of (0.2-0.5): 1, mixing;
the catalyst in the step (1) is formed by mixing dibutyl tin dilaurate and tetrabutyl titanate, wherein the mass ratio of the dibutyl tin dilaurate to the tetrabutyl titanate is (0.5-0.8): 1, a step of;
the mole ratio of the dibasic acid, the dihydric alcohol and the catalyst in the step (1) is 100: (120-160): (0.5-2).
2. The method of producing a degradable copolyester hot melt adhesive according to claim 1, wherein the reaction temperature of the esterification reaction in the step (1) is 160 to 180 ℃.
3. The method for preparing the degradable copolyester hot melt adhesive according to claim 1, wherein the antioxidant in the step (2) is at least one of antioxidant 1010, antioxidant 164 and antioxidant TNP.
4. The method for preparing a degradable copolyester hot melt adhesive according to claim 1, wherein the temperature of the polycondensation reaction in the step (2) is 190-230 ℃ and the pressure is 100-200Pa.
5. A degradable copolyester hot melt adhesive, which is characterized by being prepared by the preparation method of the degradable copolyester hot melt adhesive as claimed in any one of claims 1 to 4.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819621A (en) * | 2014-01-24 | 2014-05-28 | 青岛科技大学 | Method for preparing itaconic acids copolyester with macromolecular network structure |
| CN107652420A (en) * | 2017-09-22 | 2018-02-02 | 昆山天洋热熔胶有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN114621424A (en) * | 2022-01-07 | 2022-06-14 | 浙江恒逸石化研究院有限公司 | Preparation method of aliphatic-aromatic linear copolyester containing itaconic acid |
| CN115572564A (en) * | 2022-10-17 | 2023-01-06 | 浙江澳宇新材料科技有限公司 | Bio-based degradable copolyester hot melt adhesive and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819621A (en) * | 2014-01-24 | 2014-05-28 | 青岛科技大学 | Method for preparing itaconic acids copolyester with macromolecular network structure |
| CN107652420A (en) * | 2017-09-22 | 2018-02-02 | 昆山天洋热熔胶有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN114621424A (en) * | 2022-01-07 | 2022-06-14 | 浙江恒逸石化研究院有限公司 | Preparation method of aliphatic-aromatic linear copolyester containing itaconic acid |
| CN115572564A (en) * | 2022-10-17 | 2023-01-06 | 浙江澳宇新材料科技有限公司 | Bio-based degradable copolyester hot melt adhesive and preparation method thereof |
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Denomination of invention: A degradable copolymer ester hot melt adhesive and its preparation method Granted publication date: 20231201 Pledgee: Agricultural Bank of China Jiangshan Branch Pledgor: Zhejiang Aoyu New Material Technology Co.,Ltd. Registration number: Y2024980006499 |