CN114605949B - Epoxy modified polyester hot melt adhesive and preparation method thereof - Google Patents
Epoxy modified polyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN114605949B CN114605949B CN202111010920.8A CN202111010920A CN114605949B CN 114605949 B CN114605949 B CN 114605949B CN 202111010920 A CN202111010920 A CN 202111010920A CN 114605949 B CN114605949 B CN 114605949B
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- hot melt
- melt adhesive
- polyester
- epoxy resin
- epoxy
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- 229920000728 polyester Polymers 0.000 title claims abstract description 65
- 239000004831 Hot glue Substances 0.000 title claims abstract description 50
- 239000004593 Epoxy Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid ester group Chemical group C(CCCCCCCCCCC)(=O)O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 8
- FANBESOFXBDQSH-UHFFFAOYSA-N Ethyladipic acid Chemical compound CCC(C(O)=O)CCCC(O)=O FANBESOFXBDQSH-UHFFFAOYSA-N 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 9
- 150000001718 carbodiimides Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000084 colloidal system Substances 0.000 abstract description 5
- 229920001225 polyester resin Polymers 0.000 abstract description 3
- 239000004645 polyester resin Substances 0.000 abstract description 3
- 230000003712 anti-aging effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 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 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- KUWCMTFKTVOJID-UHFFFAOYSA-N 1,2-icosanediol Chemical compound CCCCCCCCCCCCCCCCCCC(O)CO KUWCMTFKTVOJID-UHFFFAOYSA-N 0.000 description 2
- JGHSBPIZNUXPLA-UHFFFAOYSA-N 2-hydroxyhexadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)C(O)=O JGHSBPIZNUXPLA-UHFFFAOYSA-N 0.000 description 2
- -1 2-methylpropyloxy Chemical group 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011835 investigation Methods 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
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OJVDNWWRBOTQHQ-UHFFFAOYSA-N 10-iodooctadecanoic acid Chemical compound CCCCCCCCC(I)CCCCCCCCC(O)=O OJVDNWWRBOTQHQ-UHFFFAOYSA-N 0.000 description 1
- IEYFRQLMJACEQY-UHFFFAOYSA-N 16-iodo-3-methylhexadecanoic acid Chemical compound OC(=O)CC(C)CCCCCCCCCCCCCI IEYFRQLMJACEQY-UHFFFAOYSA-N 0.000 description 1
- KLNKMGPJWOMQTJ-UHFFFAOYSA-N 2,5-diaminohexanedioic acid Chemical compound OC(=O)C(N)CCC(N)C(O)=O KLNKMGPJWOMQTJ-UHFFFAOYSA-N 0.000 description 1
- ZJQZWNLKRBUEKX-UHFFFAOYSA-N 2,5-dianilinoterephthalic acid Chemical compound OC(=O)C=1C=C(NC=2C=CC=CC=2)C(C(=O)O)=CC=1NC1=CC=CC=C1 ZJQZWNLKRBUEKX-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- PXWAQUODOTWYMT-UHFFFAOYSA-N 2-Hexylglycerol Chemical compound CCCCCCOC(CO)CO PXWAQUODOTWYMT-UHFFFAOYSA-N 0.000 description 1
- HXKXBCBZXXQPPD-UHFFFAOYSA-N 2-bromododecanoic acid Chemical compound CCCCCCCCCCC(Br)C(O)=O HXKXBCBZXXQPPD-UHFFFAOYSA-N 0.000 description 1
- YVOMYDHIQVMMTA-UHFFFAOYSA-N 3-Hydroxyadipic acid Chemical compound OC(=O)CC(O)CCC(O)=O YVOMYDHIQVMMTA-UHFFFAOYSA-N 0.000 description 1
- SHQRLYGZJPBYGJ-UHFFFAOYSA-N 3-decoxypropane-1,2-diol Chemical compound CCCCCCCCCCOCC(O)CO SHQRLYGZJPBYGJ-UHFFFAOYSA-N 0.000 description 1
- LHSCNQRBIIDZCB-UHFFFAOYSA-N 3-tert-butyladipic acid Chemical compound OC(=O)CC(C(C)(C)C)CCC(O)=O LHSCNQRBIIDZCB-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the field of C09J123/14, in particular to an epoxy modified polyester hot melt adhesive and a preparation method thereof, wherein the preparation raw materials comprise the following components in percentage by weight: 50-95% of polyester base material, 1-10% of epoxy resin, 0.5-2% of curing agent and 1-5% of auxiliary agent. The polyester hot melt adhesive disclosed by the invention has proper viscosity while maintaining excellent hydrolysis resistance stability, is not coated unevenly or can not be coated due to overlarge colloid viscosity or is not too small in viscosity to show obvious fluidity when being applied to the surface of a substrate, can maintain stability of effect under high temperature and high humidity by adding a compatibilizer, has excellent anti-aging strength, can promote the compatibility of polyester and epoxy resin by adding a specific end-capping agent, and solves the problem of poor thermal stability caused by carbodiimide in the prior art.
Description
Technical Field
The invention relates to the field of C09J123/14, in particular to an epoxy modified polyester hot melt adhesive and a preparation method thereof.
Background
Hot melt adhesives are adhesives that melt upon heating and cure rapidly at room temperature in a variety of fields, exist in solid form when unheated, and are formed into various shapes such as sticks, sheets, etc. to accommodate application and storage. Polyester hot melt adhesives are one of the common hot melt adhesives, and have excellent water resistance, adhesiveness and toughness, however, in practical situations, the melt viscosity of the polyester hot melt adhesives is too high, the ductility and molding processability of the coating are poor during application, the polyester hot melt adhesives are easy to adhere in a coating rod or a container in a lump, and in addition, as terminal groups in the polyester structure are carboxyl groups and hydroxyl groups with good hydrophilicity respectively, moisture can be absorbed in a humid environment, so that the colloid is denatured. In the prior art, carbodiimide substances are generally used as end-capping agents to improve the defect that colloid is easy to absorb water, but carbodiimide is expensive, has extremely poor thermal stability and is not an ideal end-capping agent.
CN101497775a discloses a method for preparing a hydrolysis-resistant polyester hot melt adhesive, and the polyester hot melt adhesive prepared by adopting 1, 4-butanediol, terephthalic acid, isophthalic acid and other substances has good hydrolysis resistance, and has lower glass transition temperature, but the water resistance is improved, and meanwhile, the colloid viscosity is synchronously increased, and the ductility and the coating property are poor.
CN105111990a discloses a preparation method of a modified polyester hot melt adhesive and an adhesive film thereof, wherein a polyurethane elastomer is adopted to modify the polyester hot melt adhesive, and a certain antioxidant is added, so that the problem of low-temperature brittleness of the hot melt adhesive is solved, but the problem of water absorption cannot be solved when the hot melt adhesive is adhered to an aluminum plate.
Therefore, the prior art cannot achieve the effects of water blocking, high-low temperature stability and aging resistance, and therefore, development of a polyester hot melt adhesive with comprehensive functions is needed to meet market demands.
Disclosure of Invention
The first aspect of the invention provides an epoxy modified polyester hot melt adhesive, which comprises the following raw materials in parts by weight: the balance of polyester base material, 1-10% of epoxy resin, 0.5-2% of curing agent and 1-5% of auxiliary agent.
As a preferred embodiment, the preparation raw materials comprise the following components in percentage by weight: the balance of polyester base material, 1-7% of epoxy resin, 0.5-2% of amine curing agent and 1-4% of auxiliary agent.
Preferably, the preparation raw materials comprise the following components in percentage by weight: 90% of polyester base material, 6% of epoxy resin, 1% of amine curing agent and 3% of auxiliary agent.
As a preferred embodiment, the polyester base material is prepared from the following raw materials in percentage by weight: 35-50% of dibasic acid, 45-55% of dihydric alcohol, 1-5% of end capping agent and 0.1-0.5% of catalyst.
Preferably, the polyester base material is prepared from the following raw materials in percentage by weight: 45% of dibasic acid, 50.8% of dihydric alcohol, 4% of end capping agent and 0.2% of catalyst.
Preferably, the dibasic acid comprises at least one of terephthalic acid, 2-ethyl adipic acid, 2, 5-dianilino terephthalic acid, 4- (2-methylpropyloxy) -1, 3-phthalic acid, 3, 5-pyridine dicarboxylic acid, 3-tert-butyl adipic acid, 2, 5-diamino adipic acid and 3-hydroxy adipic acid.
Preferably, the dibasic acid is terephthalic acid or 2-ethyl adipic acid.
Preferably, the mass ratio of the terephthalic acid to the 2-ethyl adipic acid is (4-10): (1-5).
Further preferably, the mass ratio of terephthalic acid to 2-ethyl adipic acid is 7:2.
preferably, the dihydric alcohol comprises at least one of 1, 6-hexanediol, triethylene glycol, 2-hexyloxypropane-1, 3-diol, 3-decyloxy-1, 2-propane diol and 1, 2-eicosane diol.
Preferably, the dihydric alcohol is 1, 6-hexanediol or triethylene glycol.
Preferably, the mass ratio of the 1, 6-hexanediol to the triethylene glycol is (3-5.4): 1.
further preferably, the mass ratio of the 1, 6-hexanediol to the triethylene glycol is 4.5:1.
the catalyst is not particularly limited in the present invention, and can be used as a catalyst for esterification reaction in the art, including but not limited to tetrabutyl titanate.
The polyester hot melt adhesive is a linear molecular structure with ester groups as polymerization units and carboxyl groups and hydroxyl groups blocked, and has high molecular cohesive energy and no organic solvent, so that the polyester hot melt adhesive becomes a popular choice for environment-friendly adhesives. However, the active groups in the polyester make the polyester extremely easy to hydrolyze at high temperature and high humidity, and the bonding effect cannot be fully exerted. According to the invention, in experimental investigation, the small molecular branched chain-containing dibasic acid and dihydric alcohol are adopted for esterification, so that the bonding strength of the hot melt adhesive can be improved; further, it was found that the weight ratio was (3-5.4): 1, 6-hexanediol and triethylene glycol can endow the esterified substance with a unique soft-hard block structure, and the bonding strength of the esterified substance to an aluminum plate substrate is enhanced.
As a preferred embodiment, the polyester binder is prepared as follows: and (3) heating the dibasic acid, the dihydric alcohol and the catalyst in the system to 100-240 ℃ for esterification reaction for 0.5-3h, continuously heating to 250-260 ℃, adding the end capping agent, vacuumizing and decompressing for copolycondensation to obtain the catalyst.
As a preferred embodiment, the epoxy resin includes at least one of bisphenol a type epoxy resin and bisphenol F type epoxy resin.
Preferably, the epoxy resin is bisphenol A epoxy resin, available from Dow, USA under the model number DER 332.
Preferably, the epoxy resin has an epoxy equivalent weight of 100-280g/eq.
Preferably, the viscosity of the epoxy resin is 400-12000cps.
The polyester hot melt adhesive can be quickly solidified in a short time to realize the bonding effect, but the high cohesion of the polyester hot melt adhesive ensures that the melt viscosity of the polyester hot melt adhesive is higher, the flow resistance on the surface of a substrate in the actual coating process is high, and the processing operation difficulty of an electronic device with higher precision requirement is higher. According to the invention, in experimental investigation, the epoxy resin is added to effectively regulate and control the melt viscosity of the polyester hot melt adhesive, so that the mobility of polyester molecular chains is improved while the cohesiveness is maintained, and the coating resistance of the polyester hot melt adhesive on the surface of a substrate is reduced; it has been unexpectedly found that the hydrolysis resistance of the polyester can be further improved by using bisphenol A type epoxy resin with an epoxy equivalent of 100-280g/eq and a viscosity of 400-12000cps, and the rate of decrease of the shear strength of the polyester hot melt adhesive after long-time action of hot water is reduced to below 7%.
As a preferred embodiment, the end-capping agent comprises a monoacid and an epoxysilane in a weight ratio of (2-4): 1.
preferably, the weight ratio of the monoacid to the epoxy silane is 3:1.
preferably, the monoacid includes at least one of an inorganic monoacid and an aliphatic monoacid.
Preferably, the monoacid is an aliphatic monoacid.
Preferably, the aliphatic monobasic acid comprises at least one of lauric acid, isooctanoic acid, pentadecanoic acid, 2-hydroxyhexadecanoic acid, 16-iodo-3-methylhexadecanoic acid, 11-prop-2-ylthioundecanoic acid, 10-iodooctadecanoic acid, and 2-bromododecanoic acid.
Further preferably, the aliphatic monobasic acid is lauric acid.
Preferably, the epoxy silane is XR-500, commercially available from Shanghai Sirun chemical technology Co.
In the prior art, carbodiimide is generally used as a capping agent to improve the hydrolysis resistance of polyester, but the carbodiimide has poor temperature resistance and is easy to generate harmful gas, so that the carbodiimide cannot be popularized and used in the field of hot melt adhesives for electronic products. According to the invention, in experimental research, aliphatic monobasic acid is used as a blocking agent, so that the density of terminal active groups of a polyester product can be reduced; however, small molecular aliphatic monoacids are sensitive to temperature change, and the end-capping effect is difficult to develop at the temperature of more than 45 ℃, so that the application of the hot melt adhesive in electronic devices which are easy to be heated locally is limited; through a large number of experimental researches, the hydrolysis trend of polyester under the conditions of high temperature and high humidity can be obviously reduced by adopting the combined action of epoxy silane and aliphatic monobasic acid, and the environmental tolerance of the hot melt adhesive is improved; it was further found that the weight ratio of monoacid to epoxysilane was (2-4): and 1, the siloxane is effectively combined with a specific embedded structure, so that the compatibility of polyester and epoxy resin is improved, and the wettability and hydrolysis resistance stability of the hot melt adhesive to a base material are improved.
As a preferred embodiment, the auxiliary agent comprises a compatibilizer and at least one of an antioxidant, an oil agent, a filler and a stabilizer.
As a preferred embodiment, the compatibilizer is a modified polycarbonate.
Preferably, the modified polycarbonate is an ABS modified polycarbonate.
Preferably, the melt flow rate (190 ℃,2.16 kg) of the ABS modified polycarbonate is 5-15g/10min.
Preferably, the ABS modified polycarbonate is Cycoloy C3650, purchased from Shenzhen technology Co., ltd.
The bisphenol A epoxy resin modified polyester base stock with specific specification can effectively improve the hydrolysis resistance of the hot melt adhesive, but the hot melt adhesive has poor high-temperature stability, is still easy to oxidize and degrade in the processing and using processes, and affects the performance. According to the invention, after many attempts, the ABS modified polycarbonate with the melting flow rate of 5-15g/10min is adopted, so that the degradation of residual low molecular substances in a system can be effectively inhibited, the mechanical strength of the polyester hot melt adhesive is further improved, the hot melt adhesive can keep the stability of lasting effect under the conditions of high temperature and high humidity, and the ageing resistance is improved.
Preferably, the auxiliary agent also comprises an oil agent, a filler and a stabilizer.
Preferably, the compatibilizer, oil, filler, stabilizer
The oil agent of the invention comprises but is not limited to paraffin, C10-C20 alkanoic acid, natural resin and synthetic resin.
Fillers described herein include, but are not limited to, fumed silica, fiberglass, diatomaceous earth.
Stabilizers described herein include, but are not limited to, hindered phenols, aromatic amines, copper salts, phosphites, thioesters.
The invention is not particularly limited to curing agents, and curing agents conventional in the art, such as amine curing agents, are selected and purchased from Changzhou Lebang composite material Co., ltd, model 593.
The second aspect of the invention provides a preparation method of an epoxy modified polyester hot melt adhesive, which comprises the following steps: (1) preparing a polyester binder; (2) Adding epoxy resin and auxiliary agent into polyester base material, melting and blending by using a double screw extruder, extruding and granulating.
Compared with the prior art, the invention has the following beneficial effects:
the polyester hot melt adhesive disclosed by the invention has proper viscosity while maintaining excellent hydrolysis resistance stability, is not coated unevenly or can not be coated due to overlarge colloid viscosity or is not too small in viscosity to show obvious fluidity when being applied to the surface of a substrate, can maintain stability of effect under high temperature and high humidity by adding a compatibilizer, has excellent anti-aging strength, can promote the compatibility of polyester and epoxy resin by adding a specific end-capping agent, and solves the problem of poor thermal stability caused by carbodiimide in the prior art.
Detailed Description
Example 1
The first aspect of the embodiment provides an epoxy modified polyester hot melt adhesive, which comprises the following preparation raw materials in percentage by weight: 90% of polyester base stock, 6% of bisphenol A epoxy resin DER 332 (the epoxy equivalent is 100-280g/eq, the viscosity is 400-12000 cps), 593% of amine curing agent and 3% of auxiliary agent.
The polyester base material is prepared from the following raw materials in percentage by weight: 45% of dibasic acid, 50.8% of dihydric alcohol, 4% of end capping agent and 0.2% of tetrabutyl titanate.
The dibasic acid is terephthalic acid and 2-ethyl adipic acid, and the mass ratio is 7:2, compounding.
The dihydric alcohol is 1, 6-hexanediol and triethylene glycol, and the mass ratio is 4.5:1.
The end capping agent is lauric acid and epoxy silane XR-500, and the weight ratio is 3:1.
The preparation method of the polyester base material comprises the following steps: and (3) heating dibasic acid, dihydric alcohol and tetrabutyl titanate to 180 ℃ in a system to carry out esterification reaction for 2 hours, continuously heating to 250 ℃, adding a blocking agent, vacuumizing and decompressing to carry out copolycondensation, thus obtaining the catalyst.
The auxiliary agent is a compatibilizer, an oil agent, a filler and a stabilizer, and the mass ratio of the auxiliary agent to the stabilizer is 1:2:2: 0.5.
The oil is paraffin, in particular chlorinated paraffin, and is purchased from Jinan Huijian chemical Co., ltd, model number 52.
The filler is glass fiber and is purchased from the high and new technology industry development district epitaxial building material factory.
The stabilizer is hindered phenol, and is purchased from Shanghai Kaijin chemical engineering Co., ltd, and the model is Irganox 1076.
The compatibilizer is Cycoloy C3650 (melt flow rate (190 ℃ C., 2.16 kg)) of 5-15g/10min.
The second aspect of the embodiment provides a method for preparing an epoxy modified polyester hot melt adhesive, which comprises the following steps: (1) preparing a polyester binder; (2) Adding epoxy resin and auxiliary agent into polyester base material, melting and blending by using a double-screw extruder, wherein the feeding temperature is 210 ℃, the melting temperature is 260 ℃, and extruding and granulating.
Comparative example 1
The first aspect of the comparative example provides an epoxy modified polyester hot melt adhesive, and the specific embodiment is the same as example 1, wherein the dibasic acid is terephthalic acid and 2-ethyl adipic acid in a mass ratio of 2:7, compounding.
In a second aspect of the comparative example, a method for preparing an epoxy modified polyester hot melt adhesive is provided, and specific embodiments are the same as in example 1.
Comparative example 2
The first aspect of the comparative example provides an epoxy modified polyester hot melt adhesive, and the specific embodiment is the same as example 1, wherein the dihydric alcohol is 1, 6-hexanediol and triethylene glycol, and the mass ratio is 1:5, compounding.
In a second aspect of the comparative example, a method for preparing an epoxy modified polyester hot melt adhesive is provided, and specific embodiments are the same as in example 1.
Comparative example 3
The first aspect of the comparative example provides an epoxy modified polyester hot melt adhesive, and the specific embodiment is the same as example 1, wherein the end capping agent is lauric acid and epoxy silane XR-500, and the weight ratio is 1: and 3, compounding.
In a second aspect of the comparative example, a method for preparing an epoxy modified polyester hot melt adhesive is provided, and specific embodiments are the same as in example 1.
Comparative example 4
The first aspect of this comparative example provides an epoxy modified polyester hot melt adhesive, the specific embodiment being the same as example 1, except that bisphenol a type epoxy resin DER 331 is selected instead of bisphenol a type epoxy resin DER 332.
In a second aspect of the comparative example, a method for preparing an epoxy modified polyester hot melt adhesive is provided, and specific embodiments are the same as in example 1.
Performance testing
The polyester hot melt adhesives of the examples and the comparative examples were mixed with a curing agent, coated on two aluminum plate substrates having a length of 25cm, a width of 20cm and a thickness of 1cm, the thickness of the coating was 0.1mm, one of the substrates was cured at room temperature, and the other substrate was hydrolyzed in a saturated steam kettle for 10 hours after being cured at room temperature, and the other substrate was dried and then tested.
180 ° peel strength test standard reference: GB/T2792-2014.
Claims (2)
1. The epoxy modified polyester hot melt adhesive is characterized by comprising the following preparation raw materials in parts by weight: 90% of polyester base material, 6% of epoxy resin, 1% of amine curing agent and 3% of auxiliary agent;
the preparation raw materials of the polyester base material comprise: 45% of dibasic acid, 50.8% of dihydric alcohol, 4% of end capping agent and 0.2% of catalyst;
the dibasic acid is terephthalic acid and 2-ethyl adipic acid, and the mass ratio is 7:2, compounding;
the dihydric alcohol is 1, 6-hexanediol and triethylene glycol, and the mass ratio is 4.5:1, compounding;
the end capping agent is lauric acid and epoxy silane XR-500, and the weight ratio is 3:1, compounding;
the epoxy resin is bisphenol A type epoxy resin, the epoxy equivalent is 100-280g/eq, and the viscosity is 400-12000cps;
the auxiliary agent comprises a compatibilizer, wherein the compatibilizer is ABS modified polycarbonate, and the melting rate is 5-15g/10min.
2. A method of preparing the epoxy modified polyester hot melt adhesive of claim 1, comprising the steps of: (1) preparing a polyester binder; (2) Adding epoxy resin and auxiliary agent into polyester base material, melting and blending by using a double screw extruder, extruding and granulating.
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| KR20010016861A (en) * | 1999-08-04 | 2001-03-05 | 신현소 | Process for producing polyester hot melt adhesive composition for fabric |
| CN101353562A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Preparation of polyester hot-melt adhesive |
| CN102558453A (en) * | 2011-11-15 | 2012-07-11 | 湖州红剑聚合物有限公司 | Mono-acid blocked unsaturated polyester resin and preparation method for same |
| CN102703013A (en) * | 2012-06-28 | 2012-10-03 | 东莞市群跃电子材料科技有限公司 | Polyester hot-melt adhesive and coating method thereof |
| CN108865036A (en) * | 2018-05-14 | 2018-11-23 | 启东鑫天鼎热熔胶有限公司 | A kind of modified poly ester hot melt adhesive and preparation method thereof |
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|---|---|---|---|---|
| KR20010016861A (en) * | 1999-08-04 | 2001-03-05 | 신현소 | Process for producing polyester hot melt adhesive composition for fabric |
| CN101353562A (en) * | 2007-07-25 | 2009-01-28 | 比亚迪股份有限公司 | Preparation of polyester hot-melt adhesive |
| CN102558453A (en) * | 2011-11-15 | 2012-07-11 | 湖州红剑聚合物有限公司 | Mono-acid blocked unsaturated polyester resin and preparation method for same |
| CN102703013A (en) * | 2012-06-28 | 2012-10-03 | 东莞市群跃电子材料科技有限公司 | Polyester hot-melt adhesive and coating method thereof |
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