CN114181654B - Biodegradable copolyester hot melt adhesive and preparation method thereof - Google Patents
Biodegradable copolyester hot melt adhesive and preparation method thereof Download PDFInfo
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- CN114181654B CN114181654B CN202111574103.5A CN202111574103A CN114181654B CN 114181654 B CN114181654 B CN 114181654B CN 202111574103 A CN202111574103 A CN 202111574103A CN 114181654 B CN114181654 B CN 114181654B
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- esterification
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 46
- 239000004831 Hot glue Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 98
- 230000032050 esterification Effects 0.000 claims abstract description 62
- -1 polysiloxane Polymers 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 20
- 229920000570 polyether Polymers 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 17
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 15
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 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 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 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 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical group [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005502 peroxidation Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 8
- 239000002861 polymer material Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 238000009933 burial Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006237 degradable polymer Polymers 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000001782 photodegradation Methods 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
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
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 a biodegradable copolyester hot melt adhesive and a preparation method thereof, comprising the following steps: carrying out esterification reaction on aliphatic dibasic acid, dihydric alcohol, polysiloxane, polyether polyol and an esterification catalyst to obtain an esterification liquid A; carrying out esterification reaction on aromatic dibasic acid, aliphatic dibasic alcohol, polysiloxane, polyether polyol and an esterification catalyst to obtain an esterification liquid B; mixing the esterification liquid A, the esterification liquid B, an esterification catalyst, a photocatalyst, a heat stabilizer and an antioxidant, and reacting for 30-50 min at the temperature of 210-230 ℃ and the low vacuum of 1000-700 Pa; then raising the temperature to 235-240 ℃ and maintaining the vacuum at 70-120 Pa for polycondensation reaction for 2-3 h; discharging while the materials are hot, and granulating and drying the materials. The invention utilizes the easy peroxidation of polyether to achieve photodegradability, and the product has excellent spinnability, tensile strength and bonding effect, and also has biodegradability and photodegradability.
Description
Technical Field
The invention belongs to the technical field of polyester hot melt adhesives, and particularly relates to a biodegradable copolyester hot melt adhesive and a preparation method thereof.
Background
Along with the continuous improvement of living standard, people are paying more attention to ecological environment quality. The continuous development of the light industry, various chemical fibers are indispensable in daily life, industrial and agricultural production of people, and the dosage is huge. The traditional chemical fiber has higher melting point and high crystallinity, and the waste is not easy to degrade, thus bringing great burden to the ecological environment. Therefore, the research on the degradable polymer material fiber has important practical significance. The degradable copolyester hot melt adhesive can be applied to composite bonding and fiber blending in multiple fields, such as non-woven fabrics, textile fibers, shoe materials, packaging materials, medical sealing boxes and the like, and is an important research direction of degradable polymer material fibers.
The existing degradable high polymer material mainly comprises a thermal oxygen degradable high polymer material, a biodegradable high polymer material and a photodegradable high polymer material. The thermal oxygen degradation polymer material has low utilization value because of higher post-treatment conditions after losing functions.
The preparation of biodegradable polymers is mostly to prepare biodegradable polymer materials by melt blending materials with biodegradability; or on the basis of the existing polyester, the biodegradability is achieved by blending microbial polyester or polysaccharide. For example, in patent document CN104514041a, particles of polybutylene terephthalate/adipate (PBAT) and polylactic acid (PLA) are blended, vacuum-dried, and then the dried particles are blended with a compatibilizer, a nucleating agent and an antioxidant, and melt-spun by a screw extruder. The photodegradable high polymer material is prepared by melting and blending a photodegradable agent and a prepared olefin or polyether ester raw material at a proper temperature through a double screw extruder. The photodegradable plastic disclosed in patent document CN111253648A is prepared by mixing inorganic nano functional powder with photodegradable agent to prepare master batch, mixing the master batch with olefin raw materials, adding various auxiliary agents, and melt blending at 170-180 ℃ by a double screw extruder. The preparation process is complex, the cost is increased, and the uniformity of the product is poor. And few copolyester fibers which are both biodegradable and photodegradable are prepared on the market at present. The invention provides a preparation method of a biodegradable and photodegradable co-acting copolyester hot melt adhesive, which has the advantages of simple process, good performance and environmental friendliness.
However, the preparation methods are complicated, the cost is high, and the uniformity of the product is poor. And few copolyester fibers which are both biodegradable and photodegradable are prepared on the market at present. In view of the above, the invention provides a preparation method of a biodegradable and photodegradable co-acting copolyester hot melt adhesive, which has the advantages of simple process, good performance and environmental friendliness.
Disclosure of Invention
The invention aims to provide a biodegradable copolyester hot melt adhesive and a preparation method thereof, and the copolyester hot melt adhesive with uniform performance and combined action of biodegradation and photodegradation is prepared by utilizing an in-situ polymerization block copolymerization process from monomers, so as to solve the problems of low degradation speed, low degradation rate, uneven product melt blending granulation performance, complex preparation process, low later melt spinning efficiency and the like of the conventional copolyester hot melt adhesive.
The aim of the invention is realized by the following technical scheme:
the preparation method of the biodegradable copolyester hot melt adhesive is characterized by comprising the following steps of:
(1) Aliphatic dibasic acid, aliphatic dihydric alcohol, polysiloxane, polyether polyol and esterification catalyst are put into an esterification reaction kettle No. 1 according to a proportion, and the reaction temperature is 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
putting aromatic dibasic acid, aliphatic dihydric alcohol, polysiloxane, polyether polyol and esterification catalyst into a No. 2 esterification reaction kettle in proportion, wherein the reaction temperature is 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Pressing the esterification liquid A and the esterification liquid B into a polycondensation reaction kettle, stirring and mixing uniformly, adding an esterification catalyst, a photocatalyst, a heat stabilizer and an antioxidant into the mixed esterification liquid, and keeping the temperature between 210 and 230 ℃ and the low vacuum of between 1000 and 700Pa for reaction for 30 to 50 minutes; then raising the temperature to 235-240 ℃ and maintaining the vacuum at 70-120 Pa for polycondensation reaction for 2-3 h;
(3) Introducing nitrogen, simultaneously releasing vacuum, discharging while the material is hot, granulating and drying to obtain the copolyester hot melt adhesive;
the aliphatic dibasic acid is as follows: one or more of 1, 4-succinic acid, 1, 5-valeric acid, pivalic acid, 1, 6-adipic acid, azelaic acid, sebacic acid and dodecanedioic acid;
the aliphatic dihydric alcohol is as follows: one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-malonic acid, 1, 4-butanediol, 1, 5-pentanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 6-hexanediol;
the aromatic dibasic acid is as follows: one or more of terephthalic acid, isophthalic acid and phthalic anhydride;
the polyether polyol is one or more of polyethylene glycol with number average molecular weight of 400-2000, polyethylene glycol copolymer and polytetrahydrofuran ether; the polysiloxane is one or more of polydimethylsiloxane, polydiethyl siloxane and polyphenyl methyl siloxane with the number average molecular weight of 200-1500;
the ratio of the number of moles of the aliphatic dibasic acid to the number of moles of the aromatic dibasic acid is (0.3 to 0.6): (0.4 to 0.7); the ratio of the moles of the aliphatic diol to the total moles of the polyether polyol and polysiloxane is (0.65 to 0.98): (0.02 to 0.35), wherein the molar ratio of the polyether polyol to the polysiloxane is: (0.5-0.7): 0.3-0.5); the ratio of the total mole number of the aliphatic dibasic acid and the aromatic dibasic acid to the total mole number of the aliphatic diol, the polyether polyol and the polysiloxane is 1: (1.2-1.6);
the esterification catalyst is one or more of tetrabutyl titanate, antimonous oxide, dibutyl tin dilaurate and zinc acetate; in the step (1), the addition amount of the esterification catalyst is 0.02-0.06% of the total mass of reactants; in the step (2), the addition amount of the esterification catalyst is 0.008-0.015% of the total mass of the reaction materials;
the heat stabilizer is triphenyl phosphate and/or trimethyl phosphate, and the addition amount is 0.007-0.05% of the total reactant mass;
the antioxidant is pentaerythritol ester (mark 1010) and/or phosphite ester (mark 168), and the addition amount is 0.05-0.2% of the total reactant mass;
the photocatalyst is cobalt acetylacetonate and/or nickel acetylacetonate, and the addition amount is 0.01-0.5% of the total reactant mass.
The invention also provides the biodegradable copolyester hot melt adhesive prepared by the preparation method of the biodegradable copolyester hot melt adhesive.
Compared with the prior art, the invention has the following advantages:
the preparation method is simple and easy to implement, takes aliphatic dihydric alcohol, aliphatic dibasic acid, aromatic dibasic acid and polysiloxane as main bodies for in-situ polymerization, and simultaneously adds polyether polyol and photocatalyst, and utilizes the easy peroxidation of polyether to ensure that the polyester can reach photodegradable performance under the condition of ultraviolet light or natural light, and the prepared copolyester hot melt adhesive has excellent spinnability, better tensile strength and bonding effect and biodegradability.
The product of the invention can be applied to fiber modification, and has the functions of increasing the strength, shaping and the like; as applied to ropes, can be blended with conventional fibers to increase the strength of the rope; and the fiber is blended with conventional fibers for spinning, and the obtained shoe cap has a shaping effect after melting.
Detailed Description
The invention is further illustrated by the following specific embodiments, which are intended to be illustrative of the invention and not limiting.
Example 1
The preparation method of the biodegradable copolyester hot melt adhesive comprises the following steps:
(1) 142g of 1,6 adipic acid, 104.3g of 1, 4-butanediol, 39.2g of polydimethylsiloxane (with the number average molecular weight of 400), 40.3g of polyethylene glycol (with the number average molecular weight of 400) and 0.08g of tetrabutyl titanate are put into a No. 1 esterification reaction kettle, and the reaction temperature is regulated to be 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
242g of terephthalic acid, 169.2g of 1,4 butanediol, 60g of polydimethylsiloxane (with the number average molecular weight of 400), 65.4g of polyethylene glycol (with the number average molecular weight of 400) and 0.13g of tetrabutyl titanate are put into a No. 2 esterification reaction kettle, and the reaction temperature is regulated to be 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Introducing nitrogen into a No. 1 esterification reaction kettle and a No. 2 esterification reaction kettle, pressing the esterification liquids A and B into a polycondensation reaction kettle, stirring and mixing uniformly, simultaneously adding 0.09g of antimonous oxide, 0.3g of triphenyl phosphate, 0.48g of pentaerythritol ester and 2.5g of cobalt acetylacetonate, keeping the temperature at 220 ℃ for carrying out low vacuum reaction for 30min, then raising the temperature to 240 ℃, keeping the vacuum at 70-120 Pa for carrying out polycondensation reaction for 2h, and extracting redundant alcohol and non-distilled water;
(3) And (3) introducing nitrogen, simultaneously releasing vacuum, discharging while the copolyester is hot, granulating and drying to obtain the copolyester hot melt adhesive, wherein a sample is marked as R1.
Example 2
The preparation method of the biodegradable copolyester hot melt adhesive comprises the following steps:
(1) 177.4g of 1,6 adipic acid, 130.8g of 1, 4-butanediol, 23.6g of polydimethylsiloxane (with the number average molecular weight of 400), 50.6g of polyethylene glycol (with the number average molecular weight of 400) and 0.09g of tetrabutyl titanate are put into a No. 1 esterification reaction kettle, and the reaction temperature is regulated to be 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
201.7g of terephthalic acid, 140.8g of 1, 4-butanediol, 24.2g of polydimethylsiloxane (with the number average molecular weight of 400), 54.4g of polyethylene glycol (with the number average molecular weight of 400) and 0.1g of tetrabutyl titanate are put into a No. 2 esterification reaction kettle, and the reaction temperature is regulated to be 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Introducing nitrogen into a No. 1 esterification reaction kettle and a No. 2 esterification reaction kettle, pressing the esterification liquids A and B into a polycondensation reaction kettle, stirring and mixing uniformly, simultaneously adding 0.08g of antimonous oxide, 0.3g of trimethyl phosphate, 0.45g of phosphite ester and 2.5g of nickel acetylacetonate, keeping the temperature at 210 ℃ for carrying out low vacuum reaction for 45min, then raising the temperature to 240 ℃, keeping the vacuum at 70-120 Pa for carrying out polycondensation reaction for 2h, and extracting redundant alcohol and non-distilled water;
(3) And (3) introducing nitrogen, simultaneously releasing vacuum, discharging while the copolyester is hot, granulating and drying to obtain the copolyester hot melt adhesive, wherein a sample is marked as R2.
Example 3
The preparation method of the biodegradable copolyester hot melt adhesive comprises the following steps:
(1) 142g of 1,6 adipic acid, 96.5g of 1, 4-butanediol, 39.2g of polydimethylsiloxane (with the number average molecular weight of 400), 75.7g of polyethylene glycol (with the number average molecular weight of 400) and 0.1g of dibutyltin dilaurate are put into a No. 1 esterification reactor, and the reaction temperature is regulated to be 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
242g of terephthalic acid, 167.5g of 1, 4-butanediol, 60g of polydimethylsiloxane (with the number average molecular weight of 400), 131.4g of polyethylene glycol (with the number average molecular weight of 400) and 0.15g of dibutyltin dilaurate are put into a No. 2 esterification reactor, and the reaction temperature is regulated to be 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Introducing nitrogen into a No. 1 esterification reaction kettle and a No. 2 esterification reaction kettle, pressing the esterification liquids A and B into a polycondensation reaction kettle, stirring and mixing uniformly, simultaneously adding 0.1g of ethylene glycol antimony, 0.33g of triphenyl phosphate, 0.48g of phosphite ester and 2.5g of nickel acetylacetonate, keeping the temperature at 230 ℃ for carrying out low vacuum reaction for 30min, then raising the temperature to 240 ℃, keeping the vacuum at 70-120 Pa for carrying out polycondensation reaction for 2h, and extracting redundant alcohol and non-distilled water;
(3) And (3) introducing nitrogen, simultaneously releasing vacuum, discharging while the copolyester is hot, granulating and drying to obtain the copolyester hot melt adhesive, wherein a sample is marked as R3.
Example 4
The preparation method of the biodegradable copolyester hot melt adhesive comprises the following steps:
(1) 142.8g of 1, 4-succinic acid, 115.1g of 1, 6-hexanediol, 13g of ethylene glycol, 49.2g of polydiethylsiloxane (with the number average molecular weight of 600), 41g of polytetrahydrofuran ether (with the number average molecular weight of 250) and 0.1g of dibutyltin dilaurate are put into a No. 1 esterification reactor, and the reaction temperature is regulated to be 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
200.8g of isophthalic acid, 121.8g of 1, 6-hexanediol, 13.9g of ethylene glycol, 52.7g of polydiethylsiloxane (with the number average molecular weight of 600), 44g of polytetrahydrofuran ether (with the number average molecular weight of 250) and 0.15g of dibutyltin dilaurate are put into a No. 2 esterification reactor, and the reaction temperature is regulated to be 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Introducing nitrogen into a No. 1 esterification reaction kettle and a No. 2 esterification reaction kettle, pressing the esterification liquids A and B into a polycondensation reaction kettle, stirring and mixing uniformly, simultaneously adding 0.087g of ethylene glycol antimony, 0.3g of trimethyl phosphate, 0.45g of pentaerythritol ester and 4g of cobalt acetylacetonate, keeping the temperature at 220 ℃ for carrying out low vacuum reaction for 40min, then raising the temperature to 238 ℃, keeping the vacuum at 70-120 Pa for carrying out polycondensation reaction for 2.5h, and extracting redundant alcohol and non-distilled water;
(3) And (3) introducing nitrogen, simultaneously releasing vacuum, discharging while the copolyester is hot, granulating and drying to obtain the copolyester hot melt adhesive, wherein a sample is marked as R4.
Example 5
The preparation method of the biodegradable copolyester hot melt adhesive comprises the following steps:
(1) 142.8g of 1, 4-succinic acid, 145g of 1, 5-pentanediol, 16.4g of polydiethylsiloxane (with the number average molecular weight of 200), 41g of polytetrahydrofuran ether (with the number average molecular weight of 250) and 0.1g of dibutyltin dilaurate are put into a No. 1 esterification reaction kettle, and the reaction temperature is regulated to be 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
200.8g of isophthalic acid, 155.2g of 1, 5-pentanediol, 17.6g of polydiethylsiloxane (with the number average molecular weight of 200), 44g of polytetrahydrofuran ether (with the number average molecular weight of 250) and 0.15g of dibutyltin dilaurate are put into a No. 2 esterification reaction kettle, and the reaction temperature is regulated to 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Introducing nitrogen into a No. 1 esterification reaction kettle and a No. 2 esterification reaction kettle, pressing the esterification liquids A and B into a polycondensation reaction kettle, stirring and mixing uniformly, simultaneously adding 0.1g of antimonous oxide, 0.3g of trimethyl phosphate and 0.45g of pentaerythritol ester, keeping the temperature at 220 ℃ for carrying out low vacuum reaction for 35min, then raising the temperature to 238 ℃, keeping the vacuum at 70-120 Pa for carrying out polycondensation reaction for 2.5h, and extracting redundant alcohol and non-distilled water;
(3) And (3) introducing nitrogen, simultaneously releasing vacuum, discharging while the copolyester is hot, granulating and drying to obtain the copolyester hot melt adhesive, wherein a sample is marked as R5.
Experimental process and test method
1. Selecting an empty space far away from trees and buildings, and exposing the sample to solar light for 30 days (10 hours per day) in the presence of fixed sun facing the south; then, after the insolated particles are buried in the soil of the natural environment for 90 days, the melt index and the peel strength of each sample are tested; the results are shown in Table 1.
2. After each sample particle is buried in the soil in the natural environment for 90 days, the melt index and the peeling strength of each sample are tested; the results are shown in Table 2.
Sample treatment: taking out the sample after the experiment is finished, cleaning, drying and melting the sample, and testing the melt index of the sample; and grinding the polyester cotton into powder, transferring the polyester cotton into polyester cotton lining cloth through a double-point process, and testing the peeling strength of the polyester cotton lining cloth. The melt index in the table is tested by a melt flow rate meter under the test condition of 160 ℃ and 2.16Kg/10min; peel strength was tested by an electronic peel strength machine.
TABLE 1 melt index and peel Strength after soil re-burial after exposure
Note that: melt index unit: g/10min; peel strength unit (N)
TABLE 2 melt index and peel Strength for direct soil burial
Note that: melt index unit: g/10min; peel strength unit (N)
As can be seen from samples 1 and 2 in table 1, as the content of aliphatic dibasic acid increases, the melt index of the degradable copolyester hot melt adhesive increases, the peel strength decreases, and the degradability is better. It can be seen from samples 1 and 3 that the better the degradability of the copolyester hot melt adhesive with increasing polyether polyol content under the same conditions of the photocatalyst. It can be seen from samples 4 and 5 that the degradation rate of the samples with the photocatalyst was much faster than that of the samples without the photocatalyst under the same conditions of the polyether polyol. The copolyester hot melt adhesive prepared by the invention has stronger peel strength and has wide application in the clothing non-woven cloth industry; after exposure or soil burying, the melt index of the copolyester hot melt adhesive is continuously increased, which indicates that the chain segment breaking molecular weight is reduced, the peeling strength is reduced, the functionalization is lost, and excellent degradability is shown.
Claims (7)
1. The preparation method of the biodegradable copolyester hot melt adhesive is characterized by comprising the following steps of:
(1) Aliphatic dibasic acid, aliphatic dihydric alcohol, polysiloxane, polyether polyol and esterification catalyst are put into an esterification reaction kettle No. 1 according to a proportion, and the reaction temperature is 150-190 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid A;
putting aromatic dibasic acid, aliphatic dihydric alcohol, polysiloxane, polyether polyol and esterification catalyst into a No. 2 esterification reaction kettle in proportion, wherein the reaction temperature is 190-230 ℃; when the distilled water amount in the esterification kettle is 95% or more of the theoretical water yield, the esterification reaction is finished to obtain an esterification liquid B;
(2) Pressing the esterification liquid A and the esterification liquid B into a polycondensation reaction kettle, stirring and mixing uniformly, adding an esterification catalyst, a photocatalyst, a heat stabilizer and an antioxidant into the mixed esterification liquid, and keeping the temperature between 210 and 230 ℃ and the low vacuum of between 1000 and 700Pa for reaction for 30 to 50 minutes; then raising the temperature to 235-240 ℃ and maintaining the vacuum at 70-120 Pa for polycondensation reaction for 2-3 h;
(3) Introducing nitrogen, simultaneously releasing vacuum, discharging while the material is hot, granulating and drying to obtain the copolyester hot melt adhesive;
the ratio of the number of moles of the aliphatic dibasic acid to the number of moles of the aromatic dibasic acid is (0.3 to 0.6): (0.4 to 0.7); the ratio of the moles of the aliphatic diol to the total moles of the polyether polyol and polysiloxane is (0.65 to 0.98): (0.02 to 0.35), wherein the molar ratio of the polyether polyol to the polysiloxane is: (0.5-0.7): 0.3-0.5); the ratio of the total mole number of the aliphatic dibasic acid and the aromatic dibasic acid to the total mole number of the aliphatic diol, the polyether polyol and the polysiloxane is 1: (1.2-1.6); the polyether polyol is polyethylene glycol with a number average molecular weight of 400 or polytetrahydrofuran ether with a number average molecular weight of 250; the polysiloxane is polydimethylsiloxane or/and polydiethylsiloxane with the number average molecular weight of 200-400; the copolyester hot melt adhesive is used for fiber modification.
2. The method for preparing the copolyester hot melt adhesive according to claim 1, wherein the aliphatic dibasic acid is: one or more of 1, 4-succinic acid, 1, 5-valeric acid, pivalic acid and 1, 6-adipic acid; the aliphatic dihydric alcohol is as follows: one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-malonic acid, 1, 4-butanediol, 1, 5-pentanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, 1, 6-hexanediol; the aromatic dibasic acid is as follows: terephthalic acid, isophthalic acid, phthalic anhydride, or a mixture thereof.
3. The method for preparing the copolyester hot melt adhesive according to claim 1, wherein the esterification catalyst is one or more of tetrabutyl titanate, antimony trioxide, dibutyl tin dilaurate and zinc acetate.
4. The method for preparing a copolyester hot melt adhesive according to claim 1, wherein in the step (1), the addition amount of the esterification catalyst is 0.02-0.06% of the total mass of reactants; in the step (2), the addition amount of the esterification catalyst is 0.008% -0.015% of the total mass of the reaction materials.
5. The method for preparing the copolyester hot melt adhesive according to claim 1, wherein the heat stabilizer is triphenyl phosphate and/or trimethyl phosphate; the antioxidant is pentaerythritol ester and/or phosphite ester; the photocatalyst is cobalt acetylacetonate and/or nickel acetylacetonate.
6. The method for preparing the copolyester hot melt adhesive according to claim 1, wherein the addition amount of the heat stabilizer is 0.007-0.05% of the total reactant mass; the addition amount of the antioxidant is 0.05-0.2% of the total reactant mass; the addition amount of the photocatalyst is 0.01-0.5% of the total reactant mass.
7. A biodegradable copolyester hot melt adhesive produced according to the preparation method of the biodegradable copolyester hot melt adhesive according to any one of claims 1 to 6.
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| DE19831366A1 (en) * | 1998-07-13 | 2000-01-27 | Inventa Ag | Deep-melting copolyester or copolyetherester hotmelt adhesives |
| US20100210745A1 (en) * | 2002-09-09 | 2010-08-19 | Reactive Surfaces, Ltd. | Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes |
| CN101649045B (en) * | 2008-08-11 | 2011-06-29 | 中国科学院化学研究所 | A kind of biodegradable polyester-polyester multi-block copolymer and its preparation method and application |
| US20130158196A1 (en) * | 2011-12-19 | 2013-06-20 | E. I. Du Pont De Nemours And Company | Aliphatic-aromatic copolyetheresters |
| US20130158168A1 (en) * | 2011-12-19 | 2013-06-20 | E I Du Pont De Nemours And Company | Aliphatic-aromatic copolyetheresters |
| CN107325272A (en) * | 2017-07-11 | 2017-11-07 | 南通协鑫热熔胶有限公司 | A kind of semiaromatic type polyester hot-melt adhesive of the block containing silicone macromolecule and preparation method thereof |
| CN109651605A (en) * | 2018-12-12 | 2019-04-19 | 上海天洋热熔粘接材料股份有限公司 | A kind of preparation method of biodegradable copolyester hot melt adhesive |
| CN110483750B (en) * | 2019-09-06 | 2021-07-09 | 四川中科兴业高新材料有限公司 | Preparation method of full-biodegradable copolyester |
| CN111849151A (en) * | 2020-06-04 | 2020-10-30 | 昆山运融新材料科技有限公司 | Photolysis nylon film |
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| US5219930A (en) * | 1990-09-21 | 1993-06-15 | Quantum Chemical Corporation | Process for converting vinyl alcohol polymers to poly(keto-esters) therefrom |
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Denomination of invention: A biodegradable copolymer ester hot melt adhesive and its preparation method Granted publication date: 20230718 Pledgee: CITIC Bank Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI DONGRUI CHEMICAL Co.,Ltd. Registration number: Y2024310000078 |
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Address after: 639 Xiasheng Road, Jinshan District, Shanghai, May 12, 2015 Patentee after: Shanghai Dongrui New Materials Co.,Ltd. Country or region after: China Address before: 639 Xiasheng Road, Jinshan District, Shanghai, May 12, 2015 Patentee before: SHANGHAI DONGRUI CHEMICAL Co.,Ltd. Country or region before: China |