CN114989772B - Polyurethane hot melt adhesive for low-hardness textiles and preparation method thereof - Google Patents
Polyurethane hot melt adhesive for low-hardness textiles and preparation method thereof Download PDFInfo
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- CN114989772B CN114989772B CN202110755551.9A CN202110755551A CN114989772B CN 114989772 B CN114989772 B CN 114989772B CN 202110755551 A CN202110755551 A CN 202110755551A CN 114989772 B CN114989772 B CN 114989772B
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- hot melt
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- polypropylene oxide
- melt adhesive
- textile
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 31
- 239000004814 polyurethane Substances 0.000 title claims abstract description 31
- 239000004831 Hot glue Substances 0.000 title claims abstract description 29
- 239000004753 textile Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- 150000002009 diols Chemical class 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000012943 hotmelt Substances 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 abstract description 2
- 239000004945 silicone rubber Substances 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 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 description 6
- 238000012360 testing method Methods 0.000 description 6
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical group CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- -1 siloxanes Chemical class 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004072 triols 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of polyurethane adhesives, and belongs to the IPC (industrial personal computer) classification number of C08G18/66, in particular to a low-hardness textile polyurethane hot melt adhesive and a preparation method thereof. The raw materials of the adhesive comprise polyether polyol, polytetrahydrofuran glycol, isocyanate and a silane coupling agent. The hot melt polyurethane adhesive disclosed by the invention has the advantages of heat stability and primary bonding performance, does not permeate textile materials, has bonding strength higher than that of a silicone rubber adhesive after solidification, and simultaneously has the characteristics of low hardness and high rebound.
Description
Technical Field
The invention relates to the technical field of polyurethane adhesives, and belongs to the IPC (industrial personal computer) classification number of C08G18/66, in particular to a low-hardness textile polyurethane hot melt adhesive and a preparation method thereof.
Background
Clothing and food residence are indispensable parts of life of people, along with the improvement of society, the requirements of people on dressing are higher and higher, the requirements on the quality of clothing are higher and higher, and underwear is taken as a natural inclusion in the clothing. The underwear is used as underwear to be directly contacted with the skin, which not only requires comfortable wearing but also is safer and more sanitary. The hot melt adhesive abandons the uncomfortable feeling caused by the metal steel ring, has the effect of stable support, reduces the pressing feeling and makes the hot melt adhesive softer and more comfortable.
Patent CN106634774a provides an alcohol-soluble environment-friendly adhesive for underwear, although the adhesive has better bonding strength and high, the adhesive forms a ring structure in the preparation process, so that the hardness of the adhesive is higher, the comfort of people in wearing is reduced, and patent CN105175674a uses a polyol comprising a small molecular polyol with molecular weight less than or equal to 400 and a macromolecular polyether polyol or polyester polyol with molecular weight of 1000-2000 as raw materials to prepare a casting agent with high hardness, and the adhesive has too high hardness to be used on the underwear or not to be used on the underwear well.
Disclosure of Invention
In order that the technical content of the invention may be better understood, the following detailed description of a preferred embodiment of the invention is incorporated.
In order to solve the technical problems, the first aspect of the invention provides a low-hardness textile polyurethane hot melt adhesive, which comprises polyether polyol, polytetrahydrofuran glycol, isocyanate and silane coupling agent.
In a preferred embodiment, the raw materials of the adhesive comprise, by weight, 40-60 parts of polyether polyol, 30-50 parts of polytetrahydrofuran glycol, 5-15 parts of isocyanate, 1-5 parts of silane coupling agent and 0.04-0.07 part of catalyst.
In a more preferred embodiment, the raw materials of the adhesive comprise, by weight, 53-58 parts of polyether polyol, 45-48 parts of polytetrahydrofuran glycol, 9-13 parts of isocyanate, 1-4 parts of silane coupling agent and 0.055-0.06 part of catalyst.
In one embodiment, the polyether polyol is a polypropylene oxide diol and/or a polypropylene oxide triol.
In a preferred embodiment, the polyether polyols are polypropylene oxide diols and polypropylene oxide triols.
In one embodiment, the polyether polyol is polypropylene oxide diol and polypropylene oxide triol in a weight ratio of 1: (8-15); preferably 1: (10-12).
In one embodiment, the polypropylene oxide diol has a number average molecular weight of 1000 to 8000.
In a preferred embodiment, the polypropylene oxide diol number average molecular weight is in the range of 2000 to 6000 (for example, polypropylene oxide diol number average molecular weight may be 2000, 4000, 6000).
In one embodiment, the polypropylene oxide triol has a number average molecular weight of 2000 to 8000.
In a preferred embodiment, the polypropylene oxide triol has a number average molecular weight of 3000 to 3000 (for example, polypropylene oxide triol may have a number average molecular weight of 3000, 5000, 6000).
In one embodiment, the polytetrahydrofuran diol has a number average molecular weight of 1000 to 3000 (for example, the polytetrahydrofuran diol may have a number average molecular weight of 1000, 2000, 3000).
In one embodiment, the isocyanate is selected from at least one of 2, 4-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate.
In a preferred embodiment, the isocyanate is 2, 4-diphenylmethane diisocyanate (MDI-50).
In one embodiment, the silane coupling agent has the structure:
wherein R is 1 ＝R 2 ＝R 3 ＝—CH 3 、—C 2 H 5 or-C 3 H 7 ，/>
In a preferred embodiment, R 1 ＝R 2 ＝R 3 ＝—C 2 H 5 、Specifically, the silane coupling agent has the structure that:
its chemical name is 3-isocyanatopropyl triethoxy silane.
The kind of the catalyst is not limited, and examples of the catalyst include dibutyltin dilaurate, organic barium, organic peptides, dimorpholinodiethyl ether, dimethylethanolamine, triethanolamine, and the like.
In a preferred embodiment, the catalyst is dimorpholinodiethyl ether.
In order to increase the oxidation resistance of the adhesive, in a preferred embodiment, the raw materials of the adhesive further comprise 0.3 to 0.4 parts by weight of an antioxidant; the antioxidant is at least one selected from the group consisting of Pasteur Irgafos 168, pasteur Irganox 1010, pasteur Irganox B225, pasteur Irganox 1076 and Pasteur Irganoxx B225.
In a preferred embodiment, the antioxidant is basf Irganox 1010.
The second aspect of the invention provides a preparation method of a low-hardness textile polyurethane hot melt adhesive, which comprises the following preparation steps:
step one: adding polypropylene oxide triol into a four-neck flask, dehydrating for 25-35min, adding a silane coupling agent, and reacting at 100-100deg.C for 2hr to obtain a material A;
step two: adding the material A, polypropylene oxide glycol and polytetrahydrofuran glycol into a reaction kettle, adding an antioxidant into the reaction kettle, dehydrating for 25-35min under the conditions of 100-110 ℃ and-0.1 MPa, and preserving heat at 90-100 ℃;
step three: under the protection of nitrogen, adding isocyanate into a reaction kettle for reaction;
step four: adding a catalyst into the reaction kettle and stirring;
step five: and after defoaming, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
In one embodiment, the dehydration conditions in step one are 110-130 ℃, -0.1MPa; preferably 120℃and-0.1 MPa.
In one embodiment, the reaction temperature in step three is 110-130 ℃ and the reaction time is 1.5-2.5hr; preferably, the reaction temperature in step three is 120℃and the reaction time is 2hr.
In one embodiment, the stirring time in step four is 10-20min; preferably 15min.
In one embodiment, the deaeration time in step five is 10-20min; preferably 15min.
In a preferred embodiment, the method for preparing the low-hardness textile polyurethane hot melt adhesive comprises the following preparation steps:
step one: adding polypropylene oxide triol into a four-neck flask, dehydrating for 30min at 120 ℃ and minus 0.1MPa, adding a silane coupling agent, and reacting for 2hr at 100-110 ℃ to obtain a material A;
step two: adding the material A, polypropylene oxide glycol and polytetrahydrofuran glycol into a reaction kettle, adding an antioxidant into the reaction kettle, dehydrating for 30min under the conditions of 120 ℃ and minus 0.1MPa, and preserving heat at 90-100 ℃;
step three: adding isocyanate into the reaction kettle under the protection of nitrogen, and reacting for 2hr at 120 ℃;
step four: adding a catalyst into the reaction kettle, and stirring for 15min;
step five: defoaming for 15min, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
The adhesive is applicable to textiles, is particularly suitable for preparing adhesive tapes for traceless underwear cloth, improves the stability of products, and has low hardness and higher rebound performance.
Compared with the prior art, the polyether polyol is used, but the prepared adhesive also has lower hardness, probably because the polypropylene oxide triol with specific molecular weight can be partially or completely blocked by the specific isocyanate-containing siloxane coupling agent to form an active intermediate containing siloxane or simultaneously containing siloxane and hydroxyl, and the active intermediate is characterized in that polypropylene oxide diol and polytetrahydrofuran diol with specific molecular weight react with each other to form the adhesive with lower hardness, and meanwhile, the epoxy group and the active intermediate can react better, so that the adhesive has better mechanical property and surface property.
The beneficial effects are that:
1. according to the invention, through specific raw materials and process design, the excellent performance of the polyurethane hot melt adhesive is maintained, and the stability and softness of the product are improved by adding the silane coupling agent modified polyether in a specific proportion;
2. the hot melt polyurethane adhesive disclosed by the invention has the advantages of heat stability and primary bonding performance, does not permeate textile materials, has bonding strength higher than that of a silicone rubber adhesive after solidification, and simultaneously has the characteristics of low hardness and high rebound.
Detailed Description
Specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the raw materials in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment 1 provides a low-hardness textile polyurethane hot melt adhesive, which is prepared by the following steps:
step one: 265.38g of polypropylene oxide triol is added into a four-neck flask, dehydrated for 30min at 120 ℃ and minus 0.1MPa, and then 6.00g of silane coupling agent is added for reaction for 2hr at 100 ℃ to obtain a material A;
step two: adding the material A, 24.00g of polypropylene oxide glycol and 240.00g of polytetrahydrofuran glycol into a reaction kettle, adding 1.80g of antioxidant into the reaction kettle, dehydrating for 30min at 120 ℃ and minus 0.1MPa, and preserving heat at 90 ℃;
step three: under the protection of nitrogen, 62.52g of isocyanate is added into the reaction kettle to react for 2 hours at 120 ℃;
step four: adding 0.30g of catalyst into the reaction kettle, and stirring for 15min;
step five: defoaming for 15min, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
The polypropylene oxide triol has a number average molecular weight of 5000; the silane coupling agent is 3-isocyanatopropyl triethoxysilane, and the brand is LINK-25; the catalyst is dimorpholinodiethyl ether; the polypropylene oxide diol has a number average molecular weight of 4000; the polytetrahydrofuran diol has a number average molecular weight of 3000; the antioxidant is basf Irganox 1010; the isocyanate is MDI-50; the catalyst is dimorpholinodiethyl ether.
The hydroxyl 18.36% of the polypropylene oxide triol was terminated by siloxane as measured by the isocyanate NCO% content test (HG/T2409-1992) and the hydroxyl number (HG/T2709-1995).
Example 2
The embodiment 2 provides a low-hardness textile polyurethane hot melt adhesive, which is prepared by the following method:
step one: 261.18g of polypropylene oxide triol is added into a four-neck flask, dehydrated for 30min at 120 ℃ and minus 0.1MPa, 18g of silane coupling agent is added into the flask, and the mixture is reacted for 2hr at 110 ℃ to obtain a material A;
step two: adding the material A, 24.00g of polypropylene oxide glycol and 240.00g of polytetrahydrofuran glycol into a reaction kettle, adding 1.80g of antioxidant into the reaction kettle, dehydrating for 30min at 120 ℃ and minus 0.1MPa, and then preserving heat at 100 ℃;
step three: under the protection of nitrogen, 54.72g of isocyanate is added into the reaction kettle to react for 2 hours at 120 ℃;
step four: adding 0.30g of catalyst into the reaction kettle, and stirring for 15min;
step five: defoaming for 15min, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
The polypropylene oxide triol has a number average molecular weight of 5000; the silane coupling agent is 3-isocyanatopropyl triethoxysilane, and the brand is LINK-25; the catalyst is dimorpholinodiethyl ether; the polypropylene oxide diol has a number average molecular weight of 4000; the polytetrahydrofuran diol has a number average molecular weight of 3000; the antioxidant is basf Irganox 1010; the isocyanate is MDI-50; the catalyst is dimorpholinodiethyl ether.
The hydroxyl groups in the polypropylene oxide triol were 55.97% blocked by siloxanes as measured by the isocyanate NCO% content test (HG/T2409-1992) and the hydroxyl number (HG/T2709-1995).
Example 3
The embodiment 3 provides a low-hardness textile polyurethane hot melt adhesive, which is prepared by the following method:
step one: 255.78g of polypropylene oxide triol is added into a four-neck flask, dehydrated for 30min at 120 ℃ and minus 0.1MPa, 31.50g of silane coupling agent is added into the flask, and the mixture is reacted for 2hr at 105 ℃ to obtain a material A;
step two: adding the material A, 24.00g of polypropylene oxide glycol and 240.00g of polytetrahydrofuran glycol into a reaction kettle, adding 1.80g of antioxidant into the reaction kettle, dehydrating for 30min at 120 ℃ and minus 0.1MPa, and preserving heat at 90 ℃;
step three: 48.12g of isocyanate is added into the reaction kettle to react for 2 hours at 120 ℃ under the protection of nitrogen;
step four: adding 0.30g of catalyst into the reaction kettle, and stirring for 15min;
step five: defoaming for 15min, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
The polypropylene oxide triol has a number average molecular weight of 5000; the silane coupling agent is 3-isocyanatopropyl triethoxysilane, and the brand is LINK-25; the catalyst is dimorpholinodiethyl ether; the polypropylene oxide diol has a number average molecular weight of 4000; the polytetrahydrofuran diol has a number average molecular weight of 3000; the antioxidant is basf Irganox 1010; the isocyanate is MDI-50; the catalyst is dimorpholinodiethyl ether.
100% of the hydroxyl groups in the polypropylene oxide triol were blocked by siloxanes as measured by the isocyanate NCO% content test (HG/T2409-1992) and the hydroxyl number (HG/T2709-1995).
Example 4
The embodiment 4 provides a low-hardness textile polyurethane hot melt adhesive, which is prepared by the following method:
step one: 269.58g of polypropylene oxide triol is added into a four-neck flask, dehydrated for 30min at 120 ℃ and minus 0.1MPa, and reacted for 2hr at 105 ℃ to obtain a material A;
step two: adding the material A, 24.00g of polypropylene oxide glycol and 240.00g of polytetrahydrofuran glycol into a reaction kettle, adding 1.80g of antioxidant into the reaction kettle, dehydrating for 30min at 120 ℃ and minus 0.1MPa, and preserving heat at 90 ℃;
step three: under the protection of nitrogen, 64.32g of isocyanate is added into the reaction kettle to react for 2 hours at 120 ℃;
step four: adding 0.30g of catalyst into the reaction kettle, and stirring for 15min;
step five: defoaming for 15min, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
The polypropylene oxide triol has a number average molecular weight of 5000; the catalyst is dimorpholinodiethyl ether; the polypropylene oxide diol has a number average molecular weight of 4000; the polytetrahydrofuran diol has a number average molecular weight of 3000; the antioxidant is basf Irganox 1010; the isocyanate is MDI-50; the catalyst is dimorpholinodiethyl ether. In this example, 3-isocyanatopropyl triethoxysilane was not used, and 0% of the hydroxyl groups 0 were blocked.
Performance testing
The low hardness textile polyurethane hot melt adhesives of examples 1-4 were tested for viscosity GB/T2794-1995, stability (120C viscosity change per hour), hardness (GB/T2411-1980), tensile deformation (GB/104001992), respectively. The test results are shown in table 1:
TABLE 1
As can be seen from the test results of Table 1, the hardness of the polyurethane hot melt adhesive prepared when the raw material does not contain 3-isocyanatopropyl triethoxysilane was too high.
Claims (4)
1. The low-hardness textile polyurethane hot melt adhesive is characterized by comprising, by weight, 40-60 parts of polyether polyol, 30-50 parts of polytetrahydrofuran glycol, 5-15 parts of isocyanate, 1-5 parts of silane coupling agent and 0.04-0.07 part of catalyst;
the polyether polyol is polypropylene oxide diol and polypropylene oxide triol;
the number average molecular weight of the polypropylene oxide glycol is 1000-8000; the number average molecular weight of the polypropylene oxide triol is 2000-8000;
the number average molecular weight of the polytetrahydrofuran diol is 1000-3000;
the silane coupling agent has the structure that:
wherein R is 1 ＝R 2 ＝R 3 ＝—CH 3 、—C 2 H 5 or-C 3 H 7 ，/>
The preparation method of the low-hardness textile polyurethane hot melt adhesive is characterized by comprising the following preparation steps:
step one: adding polypropylene oxide triol into a four-neck flask, dehydrating for 25-35min, adding a silane coupling agent, and reacting at 100-100deg.C for 2hr to obtain a material A;
step two: adding the material A, polypropylene oxide glycol and polytetrahydrofuran glycol into a reaction kettle, adding an antioxidant into the reaction kettle, dehydrating for 25-35min under the conditions of 100-110 ℃ and-0.1 MPa, and preserving heat at 90-100 ℃;
step three: under the protection of nitrogen, adding isocyanate into a reaction kettle for reaction;
step four: adding a catalyst into the reaction kettle and stirring;
step five: and after defoaming, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
2. The low hardness textile polyurethane hot melt adhesive of claim 1, wherein said isocyanate is selected from at least one of 2, 4-diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate.
3. The low hardness textile polyurethane hot melt adhesive of claim 1, wherein the raw materials of the adhesive further comprise 0.3 to 0.4 parts by weight of an antioxidant.
4. A process for the preparation of a low hardness textile polyurethane hot melt adhesive according to any one of claims 1 to 3, comprising the following preparation steps:
step one: adding polypropylene oxide triol into a four-neck flask, dehydrating for 25-35min, adding a silane coupling agent, and reacting at 100-100deg.C for 2hr to obtain a material A;
step two: adding the material A, polypropylene oxide glycol and polytetrahydrofuran glycol into a reaction kettle, adding an antioxidant into the reaction kettle, dehydrating for 25-35min under the conditions of 100-110 ℃ and-0.1 MPa, and preserving heat at 90-100 ℃;
step three: under the protection of nitrogen, adding isocyanate into a reaction kettle for reaction;
step four: adding a catalyst into the reaction kettle and stirring;
step five: and after defoaming, discharging, and sealing and packaging to obtain the low-hardness textile polyurethane hot melt adhesive.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175674A (en) * | 2015-08-04 | 2015-12-23 | 航天材料及工艺研究所 | High hardness and high toughness polyurethane casting adhesive and application thereof |
| CN106189992A (en) * | 2016-07-19 | 2016-12-07 | 重庆中科力泰高分子材料股份有限公司 | The roof of the vehicle preparation method of solvent-free moisture cure urethanes adhesive |
| CN106279614A (en) * | 2016-08-30 | 2017-01-04 | 江苏凯伦建材股份有限公司 | A kind of silicane-modified polyurethane fluid sealant performed polymer and preparation method thereof and fluid sealant |
| CN106366228A (en) * | 2016-08-31 | 2017-02-01 | 江苏李文甲化工有限公司 | Polyacrylic emulsion transparent waterproof glue and preparation method thereof |
| CN106634774A (en) * | 2016-11-22 | 2017-05-10 | 重庆中科力泰高分子材料股份有限公司 | A preparing method of an alcohol-soluble environmentally friendly type adhesive used for underwear |
| CN110194944A (en) * | 2019-06-20 | 2019-09-03 | 佛山南宝高盛高新材料有限公司 | A kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and preparation method thereof |
| CN110591047A (en) * | 2019-09-10 | 2019-12-20 | 华南理工大学 | A kind of degradable polyether polyurethane and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3394135A1 (en) * | 2015-12-23 | 2018-10-31 | Sika Technology AG | Polyurethane hot melt adhesive based on polyacrylates with high heat resistance |
-
2021
- 2021-07-05 CN CN202110755551.9A patent/CN114989772B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175674A (en) * | 2015-08-04 | 2015-12-23 | 航天材料及工艺研究所 | High hardness and high toughness polyurethane casting adhesive and application thereof |
| CN106189992A (en) * | 2016-07-19 | 2016-12-07 | 重庆中科力泰高分子材料股份有限公司 | The roof of the vehicle preparation method of solvent-free moisture cure urethanes adhesive |
| CN106279614A (en) * | 2016-08-30 | 2017-01-04 | 江苏凯伦建材股份有限公司 | A kind of silicane-modified polyurethane fluid sealant performed polymer and preparation method thereof and fluid sealant |
| CN106366228A (en) * | 2016-08-31 | 2017-02-01 | 江苏李文甲化工有限公司 | Polyacrylic emulsion transparent waterproof glue and preparation method thereof |
| CN106634774A (en) * | 2016-11-22 | 2017-05-10 | 重庆中科力泰高分子材料股份有限公司 | A preparing method of an alcohol-soluble environmentally friendly type adhesive used for underwear |
| CN110194944A (en) * | 2019-06-20 | 2019-09-03 | 佛山南宝高盛高新材料有限公司 | A kind of structural type antibacterial moisture-curable polyurethane hot melt adhesive and preparation method thereof |
| CN110591047A (en) * | 2019-09-10 | 2019-12-20 | 华南理工大学 | A kind of degradable polyether polyurethane and preparation method thereof |
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